Metal-containing film-forming compound, metal-containing film-forming composition, and pattern forming method

Abstract

The invention relates to a compound for forming a metal-containing film, a composition for forming a metal-containing film, and a pattern forming method. The present invention addresses the problem of providing a compound for forming a metal-containing film that has excellent dry etching resistance and also has a high degree of landfill / planarization characteristics. A metal-containing film-forming composition containing the compound; and a pattern forming method using the composition. The solution of the present invention is a metal-containing compound for forming a film, which is characterized in that the compound is represented by general formula (M). In the general formula (M), R1 and R2 are each independently an organic group or a halogen atom, and W is a divalent organic group represented by the following general formula (W-1) or (W-2).

Description

Technical Field

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

[0002] With the high integration and high speed of LSI, the miniaturization of pattern rules has been progressing rapidly. As for the most advanced miniaturization technology, ArF immersion lithography is applied to the mass production of devices after the 45nm node. In addition, along with ArF immersion exposure, the double exposure (double patterning) process has been put into practical use in the generation after the 28nm node, and even narrow pitch patterns beyond the optical limit can be formed.

[0003] Then, in the manufacturing of devices after the 20nm node, research is underway on a multi-exposure (multi-patterning) process that repeats exposure and etching three or more times to create patterns with narrower pitches. However, the multi-exposure process increases the number of steps, which leads to a decrease in productivity and a significant increase in cost due to the prolonged manufacturing period and the increased frequency of defects.

[0004] In recent years, vacuum ultraviolet (EUV) lithography with a wavelength of 13.5 nm has attracted attention as a powerful technology to replace the combination of ArF immersion lithography and multiple exposure processes. By using this technology, fine patterns with a half-pixel length of less than 25 nm can be formed with a single exposure.

[0005] On the other hand, in EUV lithography, in order to compensate for the insufficient output of the light source, the resist material is strongly required to be highly sensitive. However, the increase in shot noise accompanying the high sensitivity leads to an increase in the edge roughness (LER, LWR) of the line pattern, so the balance between high sensitivity and low edge roughness can be listed as one of the important issues in EUV lithography.

[0006] In recent years, some people have studied the use of metal materials in resist materials in order to increase the sensitivity of resists and reduce the influence of shot noise. Compounds containing metal elements such as barium, titanium, hafnium, zirconium, and tin have a high absorbance for EUV light compared to organic materials that do not contain metals, and can be expected to improve the photosensitivity of resists and suppress the influence of shot noise. In addition, by combining a metal-containing resist pattern with an underlying film composed of a non-metallic material, it is expected that etching processing with a high selectivity ratio can be achieved.

[0007] For example, resist materials to which metal salts or organometallic complexes are added as described in Patent Documents 1 and 2, and non-chemically amplified resist materials using nanoparticles of metal oxides as described in Patent Documents 3 and 4 have been studied.

[0008] Among them, molecules containing tin have excellent absorption of electron beams and extreme ultraviolet rays, so some people have conducted active research. In the case of one of them, organic tin polymers, the alkyl ligands will dissociate due to light absorption or the secondary electrons generated by it, and through crosslinking formed by bonding with the oxo groups of the surrounding chains, negative tone patterning that cannot be removed by organic developers can be achieved. This type of organic tin polymer system can improve sensitivity while maintaining resolution and line edge roughness, but has not yet reached the level of commercialization (Patent Document 5). In addition, there are a lot of residual issues such as insufficient storage stability regarding changes in resist sensitivity.

[0009] In response to the above-mentioned problems, some people have also studied the development of materials containing metal elements such as titanium, hafnium, zirconium, and tin in the resist underlayer film. Performance improvements such as improvement of exposure sensitivity and suppression of sensitivity changes under storage environment, which are issues in metal-containing resist materials, are not necessary. By including the above-mentioned metal elements, it is possible to provide a resist underlayer film with excellent dry etching resistance. In Patent Document 6, it is reported that materials using Ti compounds have excellent dry etching resistance to CHF3 / CF4 gas and CO2 / N2 gas.

[0010] On the other hand, the problems when using metal compounds in resist underlayer films include, for example, embedding properties. Although embedding properties are not mentioned in Patent Document 6, generally speaking, metal oxide compounds have large thermal shrinkage during baking, and will induce significant deterioration of filling properties after high-temperature baking, so there is a doubt that they are insufficient as resist underlayer film materials that require high levels of planarization properties, embedding properties, and heat resistance. Although Patent Document 7 reports that metal compounds modified with specific ligands have excellent embedding properties, the baking temperature for the embedding property evaluation is a low temperature of 150°C, which is insufficient for resist underlayer films that require heat resistance (for example, properties to cope with heat treatment that is sometimes performed after the formation of the resist underlayer film). Patent document 8 provides an anti-etching underlayer film material with excellent filling properties after baking at 400°C by mixing the metal compound reported in patent document 7 with an organic polymer of a specific structure. However, since it is a mixed composition of a metal compound as an inorganic substance and a polymer as an organic substance, there are concerns about poor film formation due to poor compatibility, deterioration of storage stability, and deterioration of dry etching resistance.

[0011] Prior art literature

[0012] Patent Literature

[0013] [Patent Document 1] Japanese Patent No. 5708521

[0014] [Patent Document 2] Japanese Patent No. 5708522

[0015] [Patent Document 3] U.S. Patent No. 9310684

[0016] [Patent Document 4] U.S. Patent Application Publication No. 2017 / 0102612

[0017] [Patent Document 5] Japanese Patent Application Publication No. 2021-162865

[0018] [Patent Document 6] Japanese Patent No. 6189758

[0019] [Patent Document 7] Japanese Patent No. 7050137

[0020] [Patent Document 8] Japanese Patent Publication No. 2022-521531 Summary of the invention

[0021] [Problems to be solved by the invention]

[0022] The present invention is made in view of the above situation, and its purpose is to provide a compound for forming a metal-containing film that has excellent dry etching resistance to known organic lower layer film materials and also has a high degree of filling / planarization characteristics; a composition for forming a metal-containing film using the compound; and a pattern forming method using the composition.

[0023] [Methods to solve the problem]

[0024] In order to solve the above problems, the present invention provides:

[0025] A metal-containing film-forming compound, characterized in that:

[0026] The compound is represented by the following general formula (M):

[0027] [Chemistry 1]

[0028]

[0029] In the general formula (M), R1 and R2 are each independently an organic group or a halogen atom, and W is a divalent organic group represented by the following general formula (W-1) or (W-2);

[0030] [Chemistry 2]

[0031]

[0032] In the general formula (W-1), l is an integer of 2 to 3, R3 and R4 are each independently a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, a hydrogen atom, or a halogen atom, or R3 and R4 on the same carbon atom together with the carbon atom to which they are bonded form a carbonyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the alkoxy group may also have an ester group or an amide group; and R3 and R4 on the same carbon atom may also be bonded to To form a ring structure, R3 and R4 on adjacent carbons may also be bonded to form a ring structure; in the general formula (W-2), R5 is each independently a substituted or unsubstituted straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, or a halogen atom, the alkyl group, the alkenyl group, the alkynyl group, and the alkoxy group may also have an ester group or an amide group, n is an integer of 0 to 1, m is an integer of 0 to 6, and * is a bonding site with -OSn.

[0033] Here, the term "heteroalkyl" refers to an alkyl group that contains one or more (e.g., one, two, three, or four) heteroatoms (e.g., oxygen, sulfur, nitrogen, boron, silicon, phosphorus) in its main chain. The heteroatom may be inserted between adjacent carbon atoms in its parent carbon chain, or between a carbon atom and its parent molecule (i.e., between bonding sites). However, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, and substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms having ester groups or amide groups are excluded.

[0034] If it is a metal-containing film-forming compound that can bond to Sn with two hydroxyl groups of catechol, diol, or α-hydroxycarboxylic acid, since the organic ligand needs to cut two bonds during sublimation, it will become a tin-containing compound with better heat resistance than a general univalent ligand compound, and the volume shrinkage that induces the deterioration of the filling property can be suppressed. In addition, since it contains two organic groups represented by R1 and R2, it can also be given thermal fluidity. Therefore, even after high-temperature baking, a metal-containing film with excellent film-forming properties, filling and planarization characteristics can be formed.

[0035] In the above general formula (M), R1 is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated 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, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms.

[0036] If R1 is as described above, free radicals will be generated due to the homolytic cleavage of the tin-carbon bond during baking, and a cross-linking reaction caused by the free radicals will occur, resulting in excellent thermal curing properties. Therefore, a metal-containing film can be formed that has excellent film-forming properties, filling and planarization properties even after high-temperature baking.

[0037] In the above general formula (M), the above R2 is preferably -OC(=O)R2' (wherein R2' is a monovalent organic group).

[0038] In the above general formula (M), if R2 is -OC(=O)R2', the symmetry of the compound structure collapses, and a metal-containing film with excellent solvent solubility can be formed. If it is -OC(=O)R2', R2' can be freely changed, so if a bulky structure is embedded, it can be expected that the solubility and thermal fluidity will be further improved, and it is also possible to make it have a more cross-linked structure, so that sublimation can be suppressed, and it can also be expected that the volume shrinkage that induces the deterioration of the filling property can be suppressed. Therefore, even after high-temperature baking, a metal-containing film with excellent film-forming properties, filling and planarization characteristics can be formed.

[0039] In the present invention, R2' is preferably the following general formula (A-1) to (A-4) or the following general formula (2) or the following general formula (3).

[0040] [Chemistry 3]

[0041]

[0042] In the general formulas (A-1) to (A-4), Y A1 , Y A2 may be the same as or different from each other, and are a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms; R A is a hydrogen atom, a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms, R A1 It is an organic group represented by the following general formula (1) in which the protecting group is released by the action of one or both of acid and heat to generate one or more hydroxyl groups or carboxyl groups, and * represents the bonding site with the carbonyl group;

[0043] [Chemistry 4]

[0044]

[0045] In the general formula (1), R A2 is an organic group whose protecting group will be removed by the action of one or both of acid and heat, and * indicates A1 or Y A2 The bond of

[0046] [Chemistry 5]

[0047]

[0048] In the general formula (2), X is a divalent organic group having 1 to 31 carbon atoms, B is the following general formula (B), and * indicates the bonding site with the carbonyl group;

[0049] [Chemistry 6]

[0050] B=*-Y B -R B (B)

[0051] In the general formula (B), Y B is a substituted or unsubstituted saturated or unsaturated divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted divalent aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted divalent aralkyl group having 7 to 31 carbon atoms, and may be bonded to an adjacent group via an oxygen atom or an NH group, R B is a hydroxyl group or any one of the structures represented by the following general formulas (B-1) to (B-3); * represents the bonding site with the carbonyl group;

[0052] [Chemistry 7]

[0053]

[0054] In the general formulas (B-1) to (B-3), R B1 is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents B The bond of

[0055] [Chemistry 8]

[0056]

[0057] In the general formula (3), X is a divalent organic group having 1 to 31 carbon atoms, C is a group represented by the following general formulas (C-1) to (C-4), and * represents the bonding site to the carbonyl group;

[0058] [Chemistry 9]

[0059]

[0060] In the general formulas (C-1) and (C-3), R C1 are each independently a hydrogen atom or a methyl group, and they may be the same or different from each other in the same formula; in (C-3) to (C-4), R C2 It is a hydrogen atom, or a substituted or unsubstituted saturated or unsaturated monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms; * indicates the bonding site to the carbonyl group.

[0061] If R2' is a structure shown in the above general formula (A-1) to (A-4), the thermal fluidity can be improved because the structure contains a bulky thermally acid unstable group. Then, when it is used in a metal-containing film-forming composition, the thermally acid unstable group will be detached during baking to generate a hydroxyl group and a carboxyl group. The OH and α-hydrogen of the carboxylic acid generated thereby will easily react with the free radicals generated by the breakage of the tin-carbon bond during baking, so a cross-linking reaction will occur, and the thermal curing property is excellent, so the volume shrinkage that induces the deterioration of the flatness and the filling property can be suppressed, and a metal-containing film with excellent film-forming properties and flattening properties / filling properties can be formed even after high-temperature baking.

[0062] Furthermore, if R2' is a structure represented by the above general formula (2), it will contain a hydroxyl group or any cross-linking group in the structures represented by the above general formulas (B-1) to (B-3) at the end. Therefore, when it is used in a metal-containing film-forming composition, it will easily react with free radicals generated by the breaking of the tin-carbon bond during baking to cause a cross-linking reaction. Even if there are only these cross-linking groups, a cross-linking reaction can be initiated. Therefore, it has excellent thermal curing properties, can suppress volume shrinkage that induces deterioration of flatness and filling properties, and can form a metal-containing film that has excellent film-forming properties and flattening properties / filling properties even after high-temperature baking.

[0063] Furthermore, if R2' is the structure represented by the above-mentioned general formula (3), since it contains the structures represented by (C-1) to (C-4), the cross-linking group density is high and the thermal curing property is excellent. Therefore, when it is used in a metal-containing film-forming composition, the volume shrinkage during baking is small, and a metal-containing film can be formed that has excellent film-forming properties and planarization properties / filling properties even after high-temperature baking.

[0064] In the present invention, Y in the general formulas (A-1) to (A-4) A1 Preferably, X in the general formula (2) or X in the general formula (3) is a substituted or unsubstituted unsaturated hydrocarbon having 2 to 20 carbon atoms.

[0065] If Y in the above general formulas (A-1) to (A-4) A1If X in the general formula (2) or X in the general formula (3) is a substituted or unsubstituted unsaturated hydrocarbon having 2 to 20 carbon atoms, the thermal curing property of the metal-containing film-forming compound can be further improved.

[0066] In the present invention, Y in the above-mentioned general formulas (A-1) to (A-4) can be provided A1 , X in the above general formula (2) or X in the above general formula (3) is a metal-containing film-forming compound of the following general formula (4).

[0067] [Chemistry 10]

[0068]

[0069] In the general formula (4), R a , R b and R C is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, R a and R b They may also be bonded to form a cyclic substituent; *1 and *2 represent the bonding sites with the carbonyl group, respectively, and the substitution positions of *1 and *2 may also be interchangeable.

[0070] If the metal-containing film-forming compound has such a structure, it is possible to achieve both thermal fluidity and thermal curing properties to a high degree, and when it is used in a metal-containing film-forming composition, a metal-containing film that exhibits more excellent planarization characteristics / filling characteristics can be formed.

[0071] The ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn of the metal-containing film-forming compound in terms of polystyrene determined by gel permeation chromatography is preferably 1.00≤Mw / Mn≤1.50.

[0072] If the metal-containing film-forming compound has a dispersion within this range, it will have better thermal fluidity, so when it is mixed with the metal-containing film-forming composition, it can not only well fill the fine structure formed on the substrate, but also form an anti-etching underlayer film that is flat across the entire substrate.

[0073] The present invention also provides a metal-containing film-forming composition which functions as a resist underlayer film material used in semiconductor manufacturing, and is characterized by containing the above-mentioned (a) metal-containing film-forming compound and (b) an organic solvent.

[0074] If such a metal-containing film-forming composition contains an organic tin compound having excellent solvent solubility, heat resistance and thermal fluidity, it can form a metal-containing film having excellent dry etching resistance compared to known organic underlayer film materials and having high filling / planarization properties.

[0075] The composition of the present invention is a metal-containing film-forming composition that can be used as a resist underlayer film used in a multilayer resist method, and may further contain one or more of (c) a crosslinking agent, (d) a surfactant, (e) a fluidity promoter, and (f) an acid generator.

[0076] Such a composition is obtained by adding the above-mentioned components to the above-mentioned metal-containing film-forming compound to impart more ideal properties, thereby achieving more ideal high-level filling and planarization properties.

[0077] In the present invention, the (b) organic solvent is preferably a mixture of one or more organic solvents having a boiling point of less than 180°C and one or more organic solvents having a boiling point of 180°C or higher.

[0078] Such a composition can be made to have a higher degree of both filling and planarization properties by giving thermal fluidity to the above-mentioned metal-containing film-forming compound by adding a high boiling point solvent. In addition, in this specification, the boiling point is a value at 1 atmosphere (1013 hPa).

[0079] Furthermore, the present invention provides a pattern forming method, which is a method for forming a pattern on a processed substrate, characterized by comprising the following steps:

[0080] (I-1) a step of applying the metal-containing film-forming composition of the present invention onto a substrate to be processed and then performing a heat treatment to form a metal-containing film;

[0081] (I-2) forming a resist upper layer film on the metal-containing film using a photoresist material;

[0082] (I-3) exposing the resist upper layer film to pattern exposure and then developing the film with a developer to form a pattern on the resist upper layer film;

[0083] (I-4) a step of transferring the pattern to the metal-containing film by dry etching using the patterned resist upper layer film as a mask; and

[0084] (I-5) A step of processing the substrate to be processed by using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0085] By using the pattern forming method using the above-mentioned two-layer resist process, a fine pattern can be formed on a workpiece (workpiece substrate).

[0086] Furthermore, the present invention is a method for forming a pattern on a processed substrate, which is characterized by comprising the following steps:

[0087] (II-1) a step of applying the metal-containing film-forming composition of the present invention onto a substrate to be processed and then performing a heat treatment to form a metal-containing film;

[0088] (II-2) a step of forming a resist intermediate film on the metal-containing film;

[0089] (II-3) forming a resist upper film on the resist intermediate film using a photoresist material;

[0090] (II-4) exposing the resist upper layer film to pattern exposure and then developing the film with a developer to form a pattern on the resist upper layer film;

[0091] (II-5) a step of transferring the pattern to the resist intermediate film by dry etching using the patterned resist upper layer film as a mask;

[0092] (II-6) a step of transferring the pattern to the metal-containing film by dry etching using the resist intermediate film to which the pattern has been transferred as a mask; and

[0093] (II-7) A step of processing the substrate to be processed by using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0094] By using the pattern forming method using the three-layer resist process, a fine pattern can be formed on a workpiece with high precision.

[0095] Furthermore, the present invention provides a pattern forming method, which is a method for forming a pattern on a processed substrate, characterized by comprising the following steps:

[0096] (III-1) a step of applying the metal-containing film-forming composition of the present invention onto a substrate to be processed and then performing a heat treatment to form a metal-containing film;

[0097] (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film on the metal-containing film;

[0098] (III-3) forming an organic thin film on the inorganic hard mask intermediate film;

[0099] (III-4) forming a resist upper layer film on the organic thin film using a photoresist material;

[0100] (III-5) exposing the resist upper layer film to pattern exposure and then developing the film with a developer to form a pattern on the resist upper layer film;

[0101] (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 patterned resist upper layer film as a mask;

[0102] (III-7) a step of transferring the pattern to the metal-containing film by dry etching using the inorganic hard mask intermediate film to which the pattern is transferred as a mask; and

[0103] (III-8) A step of processing the substrate to be processed by using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0104] By using the pattern forming method using the above-mentioned four-layer resist process, a fine pattern can be formed on the workpiece with high precision.

[0105] At this time, the inorganic hard mask is preferably formed by a CVD method or an ALD method.

[0106] If the inorganic hard mask is formed by a CVD method or an ALD method, a fine pattern can be formed on the workpiece with higher precision.

[0107] Furthermore, the present invention is a method for forming a pattern on a processed substrate, which is characterized by comprising the following steps:

[0108] (IV-1) forming a resist underlayer film on a substrate to be processed;

[0109] (IV-2) a step of coating the metal-containing film-forming composition of the present invention on the resist underlayer film and then performing a heat treatment to form a metal-containing film;

[0110] (IV-3) a step of forming a resist upper layer film on the metal-containing film using a photoresist material; or a step of forming a contact film on the metal-containing film by spin coating and forming a resist upper layer film thereon using a photoresist material;

[0111] (IV-4) exposing the resist upper layer film to pattern exposure and then developing the film with a developer to form a pattern on the resist upper layer film;

[0112] (IV-5) a step of transferring the pattern to the metal-containing film, or the adhesive film and the metal-containing film, by dry etching using the patterned resist upper layer film as a mask;

[0113] (IV-6) a step of 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

[0114] (IV-7) A step of processing the substrate to be processed using the patterned resist underlayer film as a mask to form a pattern on the substrate to be processed.

[0115] By using the pattern forming method using the multilayer resist process, a fine pattern can be formed on a workpiece with high precision.

[0116] Furthermore, the present invention provides a pattern forming method, which is a method for forming a pattern on a processed substrate, characterized by comprising the following steps:

[0117] (V-1) forming a resist underlayer film on a substrate to be processed;

[0118] (V-2) forming a resist intermediate film, or a combination of an inorganic hard mask intermediate film selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film and an organic thin film on the resist underlayer film;

[0119] (V-3) a step of forming a resist upper film using a photoresist material on the resist intermediate film or the combination of the inorganic hard mask intermediate film and the organic thin film;

[0120] (V-4) exposing the resist upper layer film to pattern exposure and then developing the film with a developer to form a pattern on the resist upper layer film;

[0121] (V-5) a step of transferring the pattern to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film by dry etching using the patterned resist upper film as a mask;

[0122] (V-6) a step of transferring the pattern to the resist underlayer film by dry etching using the resist interlayer film or the inorganic hard mask interlayer film to which the pattern has been transferred as a mask;

[0123] (V-7) a step of coating the metal-containing film-forming composition of the present invention on the resist underlayer film having the pattern formed thereon, and then covering the metal-containing film by heat treatment to fill the space between the resist underlayer film patterns with the metal-containing film;

[0124] (V-8) etching back the metal-containing film coated on the resist underlayer film having the pattern formed thereon by chemical stripping agent or dry etching to expose the top surface of the resist underlayer film having the pattern formed thereon;

[0125] (V-9) removing the resist intermediate film or the inorganic hard mask intermediate film remaining on the top surface of the resist underlayer film by dry etching;

[0126] (V-10) removing the resist underlayer film having the pattern formed on the surface exposed by dry etching, thereby forming a reverse pattern of the original pattern on the metal-containing film;

[0127] (V-11) A step of processing the substrate to be processed by using the metal-containing film forming the reverse pattern as a mask to form a reverse pattern on the substrate to be processed.

[0128] By using the pattern forming method using the above-mentioned reverse process, a fine pattern can be formed on the workpiece with higher precision.

[0129] In this case, it is also ideal to form the inorganic hard mask by CVD or ALD.

[0130] If the inorganic hard mask is formed by a CVD method or an ALD method, a fine pattern can be formed on the workpiece with higher precision.

[0131] [Effects of the Invention]

[0132] As described above, the metal-containing film-forming compound of the present invention is a metal-containing film-forming compound having excellent heat resistance, as shown in the above general formula (M), in which two hydroxyl groups of catechol, diol, or α-hydroxycarboxylic acid are bonded to Sn. Since it contains two other organic groups, it becomes a metal-containing film-forming compound having excellent thermal fluidity, and the performance can be adjusted by changing the structure of its organic group. When it is used in a metal-containing film-forming composition, the volume shrinkage that induces the deterioration of the embedding property can be suppressed, and a metal-containing film such as a resist underlayer film material having excellent film-forming properties and flattening properties / embedding properties can be formed even after high-temperature baking.

[0133] In particular, in the fine patterning process using the multilayer resist method in the semiconductor device manufacturing steps, even on the processed substrate with a dense portion of a high aspect ratio fine pattern structure represented by a DRAM memory where miniaturization is progressing and has a portion that is difficult to fill / flatten, filling can be performed without causing undesirable conditions such as pores and peeling. Moreover, compared with the known coating-type organic resist underlayer material, it has excellent dry etching resistance, so compared with the organic resist underlayer film, it can form a fine pattern on the processed body with higher precision.

[0134] Furthermore, the metal-containing film-forming composition comprising the metal-containing film-forming compound of the present invention contains tin atoms that have a large absorption of EUV light, and therefore has a sensitization effect due to secondary electrons generated thereby during exposure. Furthermore, since the tin atoms have a large atomic weight, the effect of inhibiting acid diffusion from the upper resist layer to the resist lower film is high, and thus has the characteristic of being able to achieve high sensitivity while generally maintaining the LWR performance that the resist upper film originally possesses. BRIEF DESCRIPTION OF THE DRAWINGS

[0135] [ Figure 1 ](A) to (F) are explanatory diagrams of an example of the pattern forming method of the present invention (three-layer resist process).

[0136] [ Figure 2 ](G) to (P) are explanatory diagrams 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).

[0137] [ Figure 3 ](Q)~(S) are illustrations of the landfill characteristic evaluation method.

[0138] [ Figure 4 ](T) and (U) are diagrams for explaining the method for evaluating the planarization characteristics. DETAILED DESCRIPTION

[0139] As described above, the present invention seeks to develop a metal-containing film-forming composition having excellent filling properties and flatness for use in a fine patterning process using a multilayer resist method in order to form a resist underlayer film that can transfer a resist pattern to a processed substrate with higher precision, and a metal-containing film-forming compound that is useful for the composition.

[0140] The inventors of this application have focused on organic tin compounds that are expected to be active in the EUV exposure generation and have repeatedly conducted intensive research. As mentioned above, tin atoms with large light absorption have a sensitization effect caused by the secondary electrons generated by them during exposure, and have the characteristics of maintaining the LWR performance that the upper film of the resist originally has while being highly sensitive. On the other hand, the organic tin compounds studied as the upper film of the resist lack heat resistance and will undergo rapid volume shrinkage during baking, so it is difficult to fill the height difference of the processed substrate and flatten it after high-temperature baking. The inventors of this application believe that if it is a diol / catechol-based compound that can be bonded to divalent tin with one molecule, the bond is not easy to break during baking and the heat resistance can be improved. In addition, it is believed that because it contains two organic groups that are unrelated to the bonding of the diol / catechol-based compound, it will become a metal-containing film-forming compound with excellent solubility and thermal fluidity, and the performance can be adjusted by appropriately adjusting the structure of its organic group.

[0141] The inventors of this application have further repeated and in-depth research and found that if the metal-containing film-forming compound is represented by the above-mentioned general formula (M), the rapid volume shrinkage during baking can be suppressed and the thermal fluidity is also excellent. Therefore, it can become a metal-containing film-forming compound with excellent film-forming properties, filling properties and planarization properties, thereby completing the present invention.

[0142] That is, the present invention is a metal-containing compound for film formation, characterized in that the compound is represented by the following general formula (M).

[0143] [Chemistry 11]

[0144]

[0145] In the general formula (M), R1 and R2 are each independently an organic group or a halogen atom, and W is a divalent organic group represented by the following general formula (W-1) or (W-2);

[0146] [Chemistry 12]

[0147]

[0148] In the general formula (W-1), l is an integer of 2 to 3, R3 and R4 are each independently a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, a hydrogen atom, or a halogen atom, or R3 and R4 on the same carbon atom together with the carbon atom to which they are bonded form a carbonyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the alkoxy group may also have an ester group or an amide group; and R3 and R4 on the same carbon atom may also be bonded to To form a ring structure, R3 and R4 on adjacent carbons may also be bonded to form a ring structure; in the general formula (W-2), R5 is each independently a substituted or unsubstituted straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, or a halogen atom, the alkyl group, the alkenyl group, the alkynyl group, and the alkoxy group may also have an ester group or an amide group, n is an integer of 0 to 1, m is an integer of 0 to 6, and * is a bonding site with -OSn.

[0149] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0150] <Metal-Containing Film-Forming Compound>

[0151] The metal-containing film-forming compound of the present invention is characterized by being represented by the following general formula (M).

[0152] [Chemistry 13]

[0153]

[0154] In the general formula (M), R1 and R2 are each independently an organic group or a halogen atom, and W is a divalent organic group represented by the following general formula (W-1) or (W-2);

[0155] [Chemistry 14]

[0156]

[0157] In the general formula (W-1), l is an integer of 2 to 3, R3 and R4 are each independently a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, a hydrogen atom, or a halogen atom, or R3 and R4 on the same carbon atom together with the carbon atom to which they are bonded form a carbonyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the alkoxy group may also have an ester group or an amide group; and R3 and R4 on the same carbon atom may also be bonded to To form a ring structure, R3 and R4 on adjacent carbons may also be bonded to form a ring structure; in the general formula (W-2), R5 is each independently a substituted or unsubstituted straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, or a halogen atom, the alkyl group, the alkenyl group, the alkynyl group, and the alkoxy group may also have an ester group or an amide group, n is an integer of 0 to 1, m is an integer of 0 to 6, and * is a bonding site with -OSn.

[0158] In the above general formula (M), R1 and R2 are each independently an organic group or a halogen group. Considering the raw material acquisition and synthesis, it is preferably an alkyl group, an ester group, an alkoxy group, or a chloro group. Considering the solvent solubility, it is more preferable that the structures are different in the same compound. In addition, if thermal fluidity is considered, it is more preferable that R1 and R2 are a combination of an alkyl group and an ester group.

[0159] In the above general formula (W-1), R3 and R4 are each independently a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, a hydrogen atom, or a halogen atom, or R3 and R4 on the same carbon together with the carbon to which they are bonded form a carbonyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the alkoxy group may also have an ester group or an amide group; and R3 and R4 on the same carbon may also be bonded to form a ring structure, and R3 and R4 on adjacent carbon atoms may also be bonded to form a ring structure, but from the viewpoint of crosslinking and heat resistance, an organic group having an unsaturated hydrocarbon group or a hydroxyl group is more desirable.

[0160] Specific examples of the above general formula when R3 and R4 are each independent of each other include the following, but are not limited to these. In the following formula, * represents an atomic bond.

[0161] [Chemistry 15]

[0162]

[0163] Specific examples of the general formula (W-1) in which both R3 and R4 are bonded to form a ring structure include the following, but are not limited to these. In the following formula, * represents an atomic bond with an oxygen atom.

[0164] [Chemistry 16]

[0165]

[0166] Both R3 and R4 on the same carbon may form a carbonyl group together with the carbon to which they are bonded. The above-mentioned alkyl, alkenyl, alkynyl, and alkoxy groups may also have an ester group or an amide group.

[0167] If both R3 and R4 on the same carbon are hydroxyl groups, they will form a geminal diol group, but if they are dehydrated, they will form a carbonyl group together with the carbon to which they are bonded. That is, the divalent organic group represented by formula (W-1) may also be a divalent organic group containing such a carbonyl group.

[0168] When R3 and R4 on the same carbon form a carbonyl group together with the carbon to which they are bonded, it is preferably an α-hydroxycarboxylic acid in which l in the above general formula (W-1) is 2. As α-hydroxycarboxylic acids, there can be mentioned any substituted compounds of glycolic acid (glycolic acid) such as lactic acid, 2-hydroxybutyric acid, tartaric acid, malic acid, citric acid, isocitric acid, mandelic acid, benzyl acid, etc. In this case, the α position of the glycolic acid may be substituted with a hydrocarbon group having 1 to 30 carbon atoms which may also contain an aromatic ring such as a benzene ring, and the aromatic ring may be further substituted with a hydroxyl group.

[0169] In the above general formula (W-1), l is an integer of 2 to 3, and is preferably 2 in view of the stability of the compound and the availability of raw materials.

[0170] The general formula (W-1) is preferably the following structure in view of raw material availability, heat resistance, and thermal fluidity. In the following formula, * represents an atomic bond with an oxygen atom.

[0171] [Chemistry 17]

[0172]

[0173] In formula (W-2), R5 is each independently a substituted or unsubstituted straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, or a halogen atom. The alkyl group, the alkenyl group, the alkynyl group, and the alkoxy group may also have an ester group or an amide group. From the perspective of heat resistance, an organic group containing an unsaturated hydrocarbon or an organic group having a hydroxyl group is more ideal.

[0174] n is an integer of 0 to 1, and m is an integer of 0 to 6. In view of raw material availability and increasing the tin content, n is preferably 0, and m is preferably 1. * is a bonding site with -OSn.

[0175] Specific examples of R5 in the general formula (W-2) include the following, but are not limited thereto. In the following formula, * represents an atomic bond to an aromatic ring.

[0176] [Chemistry 18]

[0177]

[0178] The general formula (W-2) is preferably the following structure in view of raw material availability, heat resistance, and thermal fluidity.

[0179] [Chemistry 19]

[0180]

[0181] In the above general formula (M), R1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated 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, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms. In view of the suppression of sublimates, an unsubstituted alkyl group having 1 to 20 carbon atoms is more desirable, and in view of the ease of obtaining raw materials, an n-butyl group is particularly desirable.

[0182] If this metal-containing compound is used for film formation, since the compound contains Sn-alkyl bonds, the bonds will break during baking to generate free radicals, so a cross-linking reaction will occur with these free radicals as the starting point. It has excellent thermal curing properties, so it is possible to form metal-containing films such as resist underlayer film materials that have excellent film-forming properties, filling properties and planarization properties even after high-temperature baking.

[0183] In the above general formula (M), from the viewpoint of solvent solubility, R2 is preferably -OC(=O)R2'.

[0184] If such a metal-containing film-forming compound is used, the compound is asymmetric and therefore has excellent solvent solubility and excellent thermal fluidity, so that a resist underlayer film with excellent planarization characteristics can be provided. If it is -OC(=O)R2', since R2' can be freely changed, the molecular weight can be increased and a cross-linked structure can be provided, so that sublimation products can be suppressed, and thus the volume shrinkage that induces deterioration of the embedding property can be suppressed, and a metal-containing film with excellent film-forming properties, embedding and planarization characteristics can be formed even after high-temperature baking.

[0185] In the above R2, R2' is preferably the following general formulas (A-1) to (A-4), the following general formula (2), or the following general formula (3).

[0186] [Chemistry 20]

[0187]

[0188] In the general formulas (A-1) to (A-4), Y A1 , Y A2 may be the same as or different from each other, and are a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms; R Ais a hydrogen atom, a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms, R A1 It is an organic group represented by the following general formula (1) in which the protecting group is released by the action of one or both of acid and heat to generate one or more hydroxyl groups or carboxyl groups, and * indicates the bonding site with the carbonyl group.

[0189] [Chemistry 21]

[0190]

[0191] In the general formula (1), R A2 is an organic group whose protecting group will be removed by the action of one or both of acid and heat, and * indicates A1 or Y A2 The bond of .

[0192] In the general formulas (A-1) to (A-4), Y A1 , Y A2 may be the same as or different from each other, and are a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms; R A is a hydrogen atom, a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms, R A1 It is an organic group represented by the above general formula (1) in which the protecting group is released by the action of one or both of acid and heat to generate one or more hydroxyl groups or carboxyl groups.

[0193] In the above general formulas (A-2) to (A-4), Y A2 The preferred structures of can be listed below, but are not limited to these. a Represents R A1 The bond of b Indicates the bond to another.

[0194] [Chemistry 22]

[0195]

[0196] In the above general formula (A-3), R AIt is a hydrogen atom, a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms. In view of the suppression of sublimates and the increase in the Sn content, a hydrogen atom is more preferable.

[0197] In the above general formula (1), R A2 The organic group from which the thermally acid-labile group is released by the action of one or both of acid and heat is preferably a tertiary hydrocarbon group, an acyl group, or a group forming an acetal structure together with an adjacent oxygen atom, and a tertiary hydrocarbon group is particularly preferred.

[0198] As for the above-mentioned tertiary hydrocarbon group, it is more desirable to have 4 to 20 carbon atoms, and it is particularly desirable to have tertiary butyl group from the viewpoint of suppressing the sublimation product caused by the thermal decomposition product and the ease of supplying the raw materials. As for specific examples, those shown below can be cited, but are not limited to these. In addition, in the following formula, * represents an atomic bond with an oxygen atom.

[0199] [Chemistry 23]

[0200]

[0201] [Chemistry 24]

[0202]

[0203] [Chemistry 25]

[0204]

[0205] [Chemistry 26]

[0206]

[0207] The acyl group is not particularly limited, and examples thereof include formyl, acetyl, propionyl, butyryl, acryloyl, methacryloyl, malonyl, benzoyl, and naphthyl.

[0208] As for the group forming the above-mentioned acetal structure, if it is an organic group that can cause the unstable group to be separated or broken due to the action of one or both of acid and heat, it is not particularly limited. As for the specific example of the group forming the above-mentioned acetal structure, those shown below can be cited, but are not limited to these. In addition, in the following formula, * represents an atomic bond with an oxygen atom.

[0209] [Chemistry 27]

[0210]

[0211] [Chemistry 28]

[0212]

[0213] [Chemistry 29]

[0214]

[0215] If such a metal-containing film-forming compound is used, it will become a metal-containing film-forming compound with excellent solvent solubility and thermal fluidity. A1 It contains thermally acid-labile groups, so when it is used in a metal-containing film-forming composition, they will be released during baking, so the tin content will increase, and it will become a metal-containing film-forming compound with excellent dry etching resistance. In addition, the hydroxyl and carboxyl groups generated by the release will easily react with the free radicals generated by the breakage of the tin-carbon bond during baking due to the presence of the terminal OH and α-hydrogen to cause a cross-linking reaction. Since it has excellent thermal curing properties, it can suppress volume shrinkage and form a metal-containing film with excellent film-forming properties and flattening properties / filling properties even after high-temperature baking.

[0216] When a metal-containing film is formed using an organic tin compound, the organic group bonded to the Sn atom separated by the C atom will be separated and a free radical will be generated during baking. The generated free radical will form a -Sn-O-Sn- bond, and a condensation polymerization reaction will begin, thereby hardening the metal-containing film. On the other hand, since the organic group will be separated at the same time as the above reaction, a large film shrinkage will occur during baking. However, the above-mentioned compounds have a thermally unstable group at the end, and the thermally unstable group will be separated during baking to generate a hydroxyl or carboxyl group. The OH and α-hydrogen at the end of them are easy to react with free radicals, and a cross-linking reaction will occur as shown in the following reaction formula. Because there are at least one or more such organic groups, the thermal decomposition and sublimation of the organic groups can be suppressed, and the thermal fluidity is excellent, so a metal-containing film with excellent filling properties can be formed.

[0217] [Chemistry 30]

[0218]

[0219] [Chemistry 31]

[0220]

[0221] In the above general formula (2), X is a divalent organic group having 1 to 31 carbon atoms, B is the following general formula (B), and * indicates the bonding site to the carbonyl group.

[0222] [Chemistry 32]

[0223] B=*-Y B -R B (B)

[0224] In the general formula (B), YB is a substituted or unsubstituted saturated or unsaturated divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms (preferably a divalent aliphatic hydrocarbon group), a substituted or unsubstituted divalent aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted divalent aralkyl group having 7 to 31 carbon atoms, and may be bonded to an adjacent group via an oxygen atom or an NH group, R B is a hydroxyl group or any one of the structures represented by the following general formulas (B-1) to (B-3). B In addition to the above R B It may further have a hydroxyl group. * indicates a bonding site with a carbonyl group.

[0225] [Chemistry 33]

[0226]

[0227] In the above general formulas (B-1) to (B-3), R B1 is a hydrogen atom or a monovalent organic group having 1 to 10 valences, q represents 0 or 1, and * represents B The bond of .

[0228] In the above general formula (2), X is a divalent organic group having 1 to 31 carbon atoms, B is the following general formula (B), and * indicates the bonding site with the carbonyl group. B is a saturated or unsaturated divalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted divalent aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted divalent aralkyl group having 7 to 31 carbon atoms, R B Preferably, it is a hydroxyl group or any one of the structures represented by the following general formulas (B-1) to (B-3). In the above general formulas (B-1) to (B-3), R B1 It is a hydrogen atom or a monovalent organic group having 1 to 10 atoms, and is preferably a hydrogen atom from the viewpoint of suppressing sublimation.

[0229] The preferred structures of the general formula (B) are as follows, but are not limited thereto. In the following formula, * represents an atomic bond to a carbonyl group. The following examples also represent possible structural isomers.

[0230] [Chemistry 34]

[0231]

[0232] If such a metal-containing film-forming compound is used, it will become a metal-containing film-forming compound with excellent solvent solubility and thermal fluidity. BIt contains hydroxyl groups or unsaturated bonds, so when it is used in a metal-containing film-forming composition, it undergoes a cross-linking reaction during baking, so it has excellent thermal curing properties. It also reacts with free radicals generated by the breaking of the tin-carbon bond, so that the cross-linking reaction is promoted and has excellent thermal curing properties. Therefore, volume shrinkage can be suppressed, and a metal-containing film with excellent film-forming properties and planarization / filling properties can be formed even after high-temperature baking.

[0233] [Chemistry 35]

[0234]

[0235] In the above general formula (3), X is a divalent organic group having 1 to 31 carbon atoms, C is one of the following general formulae (C-1) to (C-4), and * indicates a bonding site with a carbonyl group.

[0236] [Chemistry 36]

[0237]

[0238] In the general formulas (C-1) and (C-3), R C1 is a hydrogen atom or a methyl group, which may be the same or different from each other in the same formula; in (C-3) to (C-4), R C2 It is a hydrogen atom, or a substituted or unsubstituted saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms. * indicates the bonding site to the carbonyl group.

[0239] In the above general formula (3), X is a divalent organic group having 1 to 31 carbon atoms, and specifically, examples thereof include a substituted or unsubstituted saturated divalent hydrocarbon group having 1 to 20 carbon atoms or an unsaturated divalent hydrocarbon group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms. C is the above general formulas (C-1) to (C-4). In (C-1) and (C-3), R C1 From the viewpoint of thermal fluidity, a methyl group is more preferable, and from the viewpoint of hardenability, a hydrogen atom is more preferable. C2 From the viewpoint of thermal fluidity, the above-described structures other than hydrogen atoms are preferred.

[0240] In the above general formulas (C-1) to (C-4), R C2 As for the preferred structure of, the following structures can be listed, but it is not limited to these. In addition, in the following formula, * represents an atomic bond with a nitrogen atom.

[0241] [Chemistry 37]

[0242]

[0243] If it is a metal-containing film-forming compound having such a structure, then because it contains the organic group represented by the above-mentioned general formula (3), it will become a metal-containing film-forming compound with excellent solvent solubility and heat resistance. Moreover, because it contains any of the structures represented by the above-mentioned general formulas (C-1) to (C-4) at the end, the cross-linking group density is high, which can reduce the rapid volume shrinkage during baking, and the thermal fluidity is also good, so that a metal-containing film with excellent filling / planarization characteristics can be formed.

[0244] In the above general formulas (A-1) to (A-4), Y A1 , X in the above general formula (2), or X in the above general formula (3) may be exemplified by the following structures, but are not limited thereto. In addition, in the following formula, * represents the bonding site to the carbon atom of the carbonyl group or * in formulas (A-1) to (A-4), (2), and (3).

[0245] [Chemistry 38]

[0246]

[0247] Y in the above general formulas (A-1) to (A-4) A1 Preferably, the metal-containing film-forming compound is characterized in that X in the above general formula (2) or X in the above general formula (3) is a substituted or unsubstituted unsaturated hydrocarbon having 2 to 20 carbon atoms.

[0248] In the above general formulas (A-1) to (A-4), Y A1 If X in the general formula (2) or X in the general formula (3) is a substituted or unsubstituted unsaturated hydrocarbon having 2 to 20 carbon atoms, the thermal curing property of the metal-containing film-forming compound can be further improved.

[0249] In addition, Y in the above general formulas (A-1) to (A-4) can be provided. A1 , X in the above general formula (2), or X in the above general formula (3) is a metal-containing film-forming compound characterized by the following general formula (4).

[0250] [Chemistry 39]

[0251]

[0252] In the general formula (4), R a , R b and R C is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, R a and R b They may also be bonded to form a cyclic substituent; *1 and *2 represent the bonding sites with the carbonyl group, respectively, and the substitution positions of *1 and *2 may also be interchangeable.

[0253] For example, the carboxylic acid raw material containing the general formula (4) can be synthesized by ring-opening the acid anhydride. However, if the asymmetric carboxylic acid anhydride is ring-opened, it will become a mixture of two types, so it will become the bonding form as described above. Due to the presence of such isomers, crystallinity can be suppressed, and it can be expected that the solvent solubility can be improved, and the flattening characteristics can be improved due to the improvement of thermal fluidity.

[0254] [Chemistry 40]

[0255]

[0256] In the above general formula (4), R a , R b and R C is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, R a and R b They may also be bonded to form a cyclic substituent, and a hydrogen atom is particularly preferred from the viewpoint of sublimation inhibition.

[0257] The metal-containing film-forming compound is preferably characterized in that a ratio Mw / Mn of a polystyrene-equivalent weight average molecular weight Mw and a number average molecular weight Mn determined by gel permeation chromatography is 1.00≤Mw / Mn≤1.50.

[0258] By definition, if it is a monomolecular compound, Mw / Mn will be 1.00, but due to the separation of the gel permeation chromatography method, there may be cases where the measured value exceeds 1.00. Generally speaking, it is extremely difficult for a polymer with repeating units to approach Mw / Mn=1.00 without using a special polymerization method. It has a distribution of Mw and Mw / Mn will become a value exceeding 1. In order to distinguish monomolecular compounds from polymers, the present invention defines 1.00≤Mw / Mn≤1.50 as an indicator of monomolecularity.

[0259] If the metal-containing film-forming compound has a dispersion within this range, the thermal fluidity will be better, so when it is mixed with the metal-containing film-forming composition, it can not only well fill the fine structure formed on the substrate, but also form an anti-etching underlayer film that is flat across the entire substrate.

[0260] <Synthesis of Metal-Containing Film-Forming Compound>

[0261] The method for obtaining the metal-containing film-forming compound of the present invention may be based on known synthesis means and is not particularly limited. For example, it can be prepared by the method described in Japanese Patent Application Laid-Open No. 5-123579 or Japanese Patent Application Laid-Open No. 52-153913.

[0262] Specifically, a Sn(IV) compound that can be derived into a target metal-containing film-forming compound (tin compound) is reacted with a diol compound such as catechol or α-hydroxycarboxylic acid or its precursor in a suitable solvent such as toluene (ligand exchange reaction, etc.), and after the reaction is terminated, the solvent and by-products are removed under appropriate conditions such as reduced pressure to obtain the target compound. If necessary, an asymmetric compound can also be obtained by adding a carboxylic acid to the above reaction.

[0263] <Metal-Containing Film-Forming Composition>

[0264] Furthermore, the present invention can provide a metal-containing film-forming composition, which functions as a resist underlayer film material used in semiconductor manufacturing, and is characterized in that it contains the above-mentioned (a) metal-containing film-forming compound and (b) an organic solvent.

[0265] If this metal-containing film-forming composition contains an organic tin compound with excellent heat resistance and thermal fluidity, it can form a metal-containing film such as a resist underlayer film material that has excellent dry etching resistance compared to known organic underlayer film materials and has a high degree of filling / planarization properties.

[0266] Hereinafter, components contained in the metal-containing film-forming composition of the present invention other than the above-mentioned (a) metal-containing film-forming compound will be described.

[0267] <(b) Organic Solvents>

[0268] 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 can dissolve or disperse the above-mentioned (a) metal-containing film-forming compound, (c) cross-linking agent, (d) surfactant, (e) fluidity promoter, (f) acid generator, other additives, etc.

[0269] Specifically, an organic solvent described in paragraphs

[0091] to

[0092] of Japanese Patent Application Laid-Open No. 2007-199653 may 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 may be preferably used.

[0270] (High boiling point solvent)

[0271] In the metal-containing film-forming composition (resist underlayer film-forming composition) of the present invention, the above-mentioned (b) organic solvent may be a mixture of one or more organic solvents having a boiling point (value under 1 atmosphere (1013 hPa)) of less than 180°C and one or more organic solvents having a boiling point of more than 180°C (high boiling point solvent).

[0272] The high boiling point solvent is not particularly limited to hydrocarbons, alcohols, ketones, esters, ethers, chlorine-based solvents, etc. as long as it can dissolve the components of the metal-containing film-forming composition of the present invention. Specific examples thereof include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 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, glycerol, 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 Alcohol methyl n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, etc., can be used alone or in combination.

[0273] The high boiling point solvent can be appropriately selected from, for example, the above-mentioned solvents in accordance with the temperature at which the metal-containing film-forming composition of the present invention is subjected to heat treatment. The boiling point of the high boiling point solvent is preferably 180°C to 300°C, and more preferably 200°C to 300°C. It is believed that if this boiling point is used, since there is no risk of volatilization becoming too fast during baking (heat treatment), sufficient thermal fluidity can be obtained during film formation, and a resist lower layer film with excellent filling / planarization characteristics can be formed. Furthermore, if this boiling point is used, since it will not remain in the film without volatilization after baking, there is no risk of adversely affecting the film properties such as etching resistance.

[0274] The amount of the organic solvent to be added is preferably in the range of 200 to 10,000 parts, more preferably 250 to 5,000 parts, based on 100 parts by mass of the (a) metal-containing film-forming compound.

[0275] When a high boiling point solvent is used, the blending amount is preferably 1 to 30 parts by mass relative to 100 parts by mass of the organic solvent having a boiling point of less than 180° C. Such a blending amount is preferred because it can provide sufficient thermal fluidity during baking, does not remain in the film, and does not cause deterioration of film properties such as etching resistance.

[0276] <Resist Underlayer Film Forming Composition>

[0277] The above composition is a metal-containing film-forming composition that can be used as a resist underlayer film used in a multilayer resist method, and may further contain one or more of (c) a crosslinking agent, (d) a surfactant, (e) a fluidity promoter, and (f) an acid generator.

[0278] Components contained in the metal-containing film-forming composition (resist underlayer film-forming composition) of the present invention other than the above-mentioned (a) metal-containing film-forming compound and (b) organic solvent will be described below.

[0279] [(c) Cross-linking agent]

[0280] In order to improve the compactness of the film and suppress the intermixing with the resist upper film, the resist lower film forming composition of the present invention may further contain (c) a crosslinking agent. As for the crosslinking agent, there is no particular limitation, and crosslinking agents of various known systems can be widely used. For example, melamine-based crosslinking agents, acrylate-based crosslinking agents, glycoluril-based crosslinking agents, benzoguanamine-based crosslinking agents, urea-based crosslinking agents, β-hydroxyalkylamide-based crosslinking agents, isocyanurate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, phenol-based crosslinking agents (e.g., hydroxymethyl or alkoxymethyl-type crosslinking agents of polynuclear phenols), epoxy-based crosslinking agents, and oxetane-based crosslinking agents can be exemplified. The content of the above-mentioned (c) crosslinking agent is preferably 5 to 50 parts by mass relative to 100 parts by mass of the above-mentioned (a) metal-containing film-forming compound, and more preferably 10 to 40 parts by mass.

[0281] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylated melamine, hexabutoxymethylated melamine, alkoxy and / or hydroxyl-substituted melamines thereof, and partial self-condensates thereof.

[0282] Specific examples of the acrylate crosslinking agent include dipentatriol hexaacrylate.

[0283] Specific examples of glycoluril-based crosslinking agents include tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, alkoxy and / or hydroxyl-substituted products thereof, and partial self-condensation products thereof.

[0284] Specific examples of the benzoguanamine-based crosslinking agent include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, alkoxy and / or hydroxyl-substituted products thereof, and partial self-condensed products thereof.

[0285] Specific examples of the urea crosslinking agent include dimethoxymethylated dimethoxyethylene urea, alkoxy and / or hydroxyl-substituted products thereof, and partial self-condensates thereof.

[0286] Specific examples of the β-hydroxyalkylamide crosslinking agent include N,N,N′,N′-tetrakis(2-hydroxyethyl)adipamide.

[0287] Specific examples of the isocyanurate-based crosslinking agent include triglycidyl isocyanurate and triallyl isocyanurate.

[0288] Specific examples of the aziridine crosslinking agent include 4,4′-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate].

[0289] Specific examples of the oxazoline crosslinking agent include 2,2'-isopropylidenebis(4-benzyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-methylenebis-4,5-diphenyl-2-oxazoline, 2,2'-methylenebis-4-phenyl-2-oxazoline, 2,2'-methylenebis-4-tert-butyl-2-oxazoline, 2,2'-bis(2-oxazoline), 1,3-phenylenebis(2-oxazoline), 1,4-phenylenebis(2-oxazoline), and 2-isopropenyloxazoline copolymers.

[0290] Specific examples of the polynuclear phenol crosslinking agent include compounds represented by the following general formula (XL-1).

[0291] [Chemistry 41]

[0292]

[0293] In the formula, S is a single bond or an S-valent hydrocarbon group having 1 to 20 carbon atoms. R6 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. s is an integer of 1 to 5.

[0294] S is a single bond or an S-valent hydrocarbon group having 1 to 20 carbon atoms. S is an integer of 1 to 5, and more preferably 2 or 3. Specific examples of S include methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, and a group obtained by removing s hydrogen atoms from eicosane. R6 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, ethylhexyl, decyl, and eicosyl, and a hydrogen atom or a methyl group is more preferred.

[0295] As for the examples of the compounds represented by the general formula (XL-1), the following compounds can be specifically exemplified. Among them, from the perspective of improving the hardening property and film thickness uniformity of the organic film, hexamethoxymethylated forms of trisphenolmethane, trisphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are more ideal. R6 is the same as above.

[0296] [Chemistry 42]

[0297]

[0298] [Chemistry 43]

[0299]

[0300] Examples of the epoxy-based crosslinking agent and the oxetane-based crosslinking agent include monomer-based and polymer-based crosslinking agents. Specific examples of the monomer-based crosslinking agent include those shown below, but are not limited to these.

[0301] [Chemistry 44]

[0302]

[0303] The above compounds are commercially available, but epoxy-based crosslinking agents and oxetane-based crosslinking agents can also be obtained by reacting a hydroxyl group with epibromopropane, 3-bromomethyloxetane, etc. as shown in the following formula. In the following formula, R is 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 aralkyl group having 7 to 31 carbon atoms. It is also possible that all hydroxyl groups are not reacted and remain. In this case, it is more ideal that the number of epoxy+oxetane>the number of hydroxyl groups, and it is more ideal that the number of epoxy+oxetane>the number of hydroxyl groups*2. The content of these compounds is more preferably 5 to 50 parts by mass, and more ideally 10 to 40 parts by mass, relative to 100 parts by mass of the above-mentioned (a) metal-containing film-forming compound.

[0304] [Chemistry 45]

[0305]

[0306] Specific examples of the compound having a hydroxyl group that can be used in the above reaction include the following, but the compound is not limited to these.

[0307] [Chemistry 46]

[0308]

[0309] As for the polymer type, specifically, there can be mentioned polymers in which the molar fraction of the repeating unit represented by the following general formula (XL-2) and (XL-3) is 20% or more. When the total molar fraction of the structural units represented by the general formula (XL-2) and (XL-3) is less than 100%, other structural units can be used in combination with α,β-unsaturated carboxylic acid esters such as other acrylic acid esters, other methacrylic acid esters, other acrylamides, other methacrylamides, crotonates, maleates, itaconic acid esters; α,β-unsaturated carboxylic acids such as methacrylic acid, acrylic acid, maleic acid, itaconic acid; acrylonitrile; methacrylonitrile; α,β-unsaturated lactones such as 5,5-dimethyl-3-methylene-2-oxotetrahydrofuran; norbornene derivatives, tetracyclo[4.4.0.1 2，5 .1 7，10] Cyclic olefins such as dodecene derivatives; α,β-unsaturated carboxylic anhydrides such as maleic anhydride and itaconic anhydride; allyl ethers; vinyl ethers; vinyl esters; vinyl silanes. Moreover, these polymers preferably have a weight average molecular weight of 1,000 to 20,000 and a GPC dispersion of 2.0 or less. Moreover, the content of these compounds is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the above-mentioned (A) metal-containing film-forming compound.

[0310] [Chemistry 47]

[0311]

[0312] In the formula, R7 is a hydrogen atom or a methyl group, R8 is a hydrogen atom or a group selected from the following formulae (2-1) to (2-3), and L1 is a single bond, -C(=O)O-, or a divalent organic group containing -C(=O)NH- or -C(=O)NCH3-.

[0313] In the general formula (XL-2), R8 preferably has the number of groups (2-1) to (2-3) > the number of hydrogen atoms in terms of curability, and more preferably has the number of groups (2-1) to (2-3) > the number of hydrogen atoms*2.

[0314] [Chemistry 48]

[0315]

[0316] In the formula, R7 is a hydrogen atom or a methyl group, and R9 is a group selected from the following formulae (2-1) to (2-3).

[0317] [Chemistry 49]

[0318]

[0319] In the above formula, the dotted lines represent atomic bonds.

[0320] <(d) Surfactant>

[0321] In the resist underlayer film forming composition of the present invention, in order to improve the coating property during spin coating, (d) surfactant may be added. As for the surfactant, those described in

[0142] to

[0147] in Japanese Patent Publication No. 2009-269953 may be used. The amount added when the surfactant is added is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the metal-containing film-forming compound (a).

[0322] <(e) Flowability Enhancer>

[0323] Furthermore, the resist underlayer film forming composition of the present invention may be further mixed with other compounds or polymers. The fluidity promoter has the function of improving the film forming property of spin coating and the filling property of substrates with height differences by mixing with the metal-containing film forming compound of the present invention. Furthermore, as for the fluidity promoter, a material with high carbon atom density and high etching resistance is more preferably used.

[0324] Examples of 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, and 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, gallol, thymol, isothymol, 4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'dimethyl-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'diallyl-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'difluoro-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'diphenyl-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'dimethoxy-4,4'-(9H-fluorene-9-ylidene) Bisphenol, 2,3,2',3'-tetrahydro-(1,1')-spirobibenzocyclopropane-6,6'-diol, 3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spirobibenzocyclopropane-6,6'-diol, 3,3,3',3',4,4'-hexamethyl-2,3,2',3'-tetrahydro-(1,1')-spirobibenzocyclopropane-6,6'-diol, 2,3,2',3'-tetrahydro-(1,1')-spirobibenzocyclopropane-5,5'-diol, 5,5'-dimethyl-3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spirobibenzocyclopropane-6,6'-diol , 1-naphthol, 2-naphthol, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, 7-methoxy-2-naphthol and dihydroxynaphthalene such as 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene and 2,6-dihydroxynaphthalene, 3-hydroxynaphthalene-2-carboxylic acid methyl ester, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthene, biphenyl, bisphenol, triphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorbornene-2-ene, α-pinene, β-pinene, limonene and other novolac resins, polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthene, polynorbornene, polycyclodecene, polytetracyclododecene, polytricyclo[2.2.1.0 2,6] heptane, poly (meth) acrylate and their copolymers. In addition, naphthol dicyclopentadiene copolymers described in Japanese Patent Publication No. 2004-205685, fluorene bisphenol novolac resins described in Japanese Patent Publication No. 2005-128509, acenaphthene copolymers described in Japanese Patent Publication No. 2005-250434, fullerenes with phenol groups described in Japanese Patent Publication No. 2006-227391, and bisphenol-A copolymers described in Japanese Patent Publication No. 2006-293298 can also be mixed. The bisphenol compound and its novolac resin described in the disclosure, the novolac resin of the adamantane phenol compound described in Japanese Patent Publication No. 2006-285095, the bisnaphthol compound and its novolac resin described in Japanese Patent Publication No. 2010-122656, the fluorene compound described in Japanese Patent Publication No. 2017-119671, the fullerene resin compound described in Japanese Patent Publication No. 2008-158002, etc. The blending amount of the above-mentioned fluidity promoter is preferably 0.001 to 100 parts by mass, more preferably 0.01 to 50 parts by mass, relative to 100 parts by mass of the metal-containing film-forming compound of the present invention.

[0325] In the resist underlayer film forming composition of the present invention, as an additive for imparting the embedding / planarizing property, for example, a liquid additive having a polyethylene glycol or polypropylene glycol structure, or a thermally decomposable polymer having a weight loss rate of 40% by mass or more at 30° C. to 250° C. and a weight average molecular weight of 300 to 200,000 can be preferably used. The thermally decomposable polymer preferably contains a repeating unit having an acetal structure represented by the following general formula (DP1) or (DP1a).

[0326] [Chemistry 50]

[0327]

[0328] In the formula, R 10 is a hydrogen atom or an optionally substituted saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms. Y is a saturated or unsaturated divalent organic group having 2 to 30 carbon atoms.

[0329] [Chemistry 51]

[0330]

[0331] In the formula, R 10a Y is an alkyl group having 1 to 4 carbon atoms. a It is a saturated or unsaturated divalent hydrocarbon group having 4 to 10 carbon atoms and may have an ether bond. n represents the average number of repeating units and is 3 to 500.

[0332] <(f) Acid Generator>

[0333] The resist underlayer film forming composition of the present invention may further promote the release reaction by adding (f) an acid generator. (f) Acid generators may generate acid by thermal decomposition or by light irradiation, and any of them may be added. Specifically, materials described in paragraphs

[0061] to

[0085] of Japanese Patent Application Publication No. 2007-199653 may be added, but the present invention is not limited to these.

[0334] The acid generator may be used alone or in combination of two or more. The amount of the acid generator added is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the metal-containing film-forming compound (a).

[0335] <Resist Underlayer Film Formation Method>

[0336] 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 photolithography or a planarizing film for semiconductor manufacturing, using the metal-containing film-forming composition.

[0337] In the method for forming a resist lower film using the metal-containing film-forming composition of the present invention, the above-mentioned metal-containing film-forming composition is applied to the processed substrate by a spin coating method or the like. By using a spin coating method or the like, good filling characteristics can be obtained. After spin coating, the solvent is evaporated, and in order to prevent mixing with the resist upper film and the resist intermediate film, baking (heat treatment) is performed to promote a cross-linking reaction. Baking is preferably performed in the range of 100°C to 600°C for 10 to 600 seconds, and more preferably in the range of 200°C to 500°C for 10 to 300 seconds. Considering the damage to the device and the influence on the deformation of the wafer, it is more ideal to set the upper limit of the heating temperature in the wafer manufacturing process of photolithography to be below 600°C, and more preferably below 500°C.

[0338] Furthermore, in the method for forming an anti-etching underlayer film using the metal-containing film-forming composition of the present invention, the metal-containing film-forming composition of the present invention can also be coated on the processed substrate by the same spin coating method as mentioned above, and the above-mentioned metal-containing film-forming composition can be calcined in a gas environment with an oxygen concentration of not less than 0.1 volume % and not more than 21 volume % to harden it, thereby forming a metal-containing film.

[0339] By calcining the metal-containing film of the present invention in this oxygen environment, a fully hardened film can be obtained. As for the gas environment in baking, it is also fine in the air, but in order to reduce oxygen, inactive gases such as N2, Ar, and He are sealed in advance, and it is more ideal to consider preventing the oxidation of the metal-containing film. In order to prevent oxidation, the oxygen concentration must be controlled, preferably below 1000ppm, and more preferably below 100ppm (volume basis). If the oxidation of the metal-containing film in baking is prevented, the absorption will increase and the etching resistance will not be reduced, so it is more ideal.

[0340] <Pattern Formation Method Using Resist Underlayer Film Forming Composition>

[0341] Furthermore, the present invention provides a pattern forming method, characterized in that, as a pattern forming method by a two-layer resist process using the above-mentioned metal-containing film-forming composition, the method has the following steps: using the above-mentioned metal-containing film-forming composition on a processed substrate to form a metal-containing film, using a photoresist material to form a resist upper film on the metal-containing film, exposing the resist upper film to a pattern, and then developing it with a developer to form a pattern on the resist upper film, using the resist upper film with the pattern formed as a mask, transferring the pattern to the metal-containing film by dry etching, using the metal-containing film with the pattern formed as a mask, processing the processed substrate to form a pattern on the processed substrate.

[0342] The resist upper layer film in the above-mentioned two-layer resist process will show resistance to etching by chlorine-based gas, so in the above-mentioned two-layer resist process, it is more ideal to use an etching gas with chlorine-based gas as the main body to perform dry etching of the metal-containing film using the resist upper layer film as a mask.

[0343] Furthermore, the present invention provides a pattern forming method, characterized in that, as a pattern forming method by a three-layer resist process using such a metal-containing film-forming composition, the method has the following steps: using the above-mentioned metal-containing film-forming composition to form a metal-containing film on a substrate to be processed, using a silicon-containing resist intermediate film material on the metal-containing film to form a silicon-containing resist intermediate film, using a photoresist material on the resist intermediate film to form a resist upper film, exposing the resist upper film to pattern exposure, and then developing it with a developer to form a pattern on the resist upper film, using the resist upper film with the pattern formed as a mask, transferring the pattern to the resist intermediate film by dry etching, using the resist intermediate film with the transferred pattern as a mask, transferring the pattern to the metal-containing film by dry etching, using the metal-containing film with the pattern formed as a mask, processing the substrate to be processed to form a pattern on the substrate to be processed.

[0344] For example, in a three-layer resist process, if Figure 1 The specific expression is as follows. In the case of a three-layer resist process, Figure 1 As shown in (A), after using the metal-containing film-forming composition of the present invention on the processed layer 2 stacked on the processed substrate 1 to form a metal-containing film (metal-containing anti-etching agent lower layer film) 3, a silicon-containing anti-etching agent intermediate film 4 is formed, and an anti-etching agent upper layer film 5 is formed thereon.

[0345] Then, if Figure 1 As shown in (B), the used portion (exposed portion) 6 of the resist upper film 5 is exposed, PEB and development are performed to form a resist upper film pattern 5a ( Figure 1 (C)). Using the obtained resist upper film pattern 5a as a mask, the silicon-containing resist intermediate film 4 is etched using CF-based gas to form a silicon-containing resist intermediate film pattern 4a ( Figure 1 (D)). After removing the resist upper film pattern 5a, the obtained silicon-containing resist intermediate film pattern 4a is used as a mask to perform chlorine plasma etching on the metal-containing film 3 to form a metal-containing film pattern (metal-containing resist lower film pattern) 3a ( Figure 1 (E)). After removing the silicon-containing resist intermediate film pattern 4a, the metal-containing film pattern 3a is used as a mask to etch the processed layer 2, forming a pattern 2a ( Figure 1 (F)).

[0346] The silicon-containing resist intermediate film in the above-mentioned three-layer resist process will show resistance to etching by chlorine-based gas and hydrogen-based gas. Therefore, in the above-mentioned three-layer resist process, it is more ideal to use an etching gas with chlorine-based gas or hydrogen-based gas as the main body to perform dry etching of the metal-containing film using the silicon-containing resist intermediate film as a mask.

[0347] For the silicon-containing resist intermediate film of the above-mentioned three-layer resist process, a polysiloxane-based intermediate film can also be preferably used. By making the silicon-containing resist intermediate film have an anti-reflection effect, reflection can be suppressed. Especially for 193nm exposure, if a material containing a large amount of aromatic groups and having a high etching selectivity with the substrate is used as an organic film, the k value will become higher and the substrate reflection will become higher, but for the silicon-containing resist intermediate film, by making it have an absorption that forms an appropriate k value, it becomes possible to suppress reflection and the substrate reflection can be set to less than 0.5%. For the silicon-containing resist intermediate film with an anti-reflection effect, anthracene can be preferably used for 248nm and 157nm exposure, and polysiloxane with a light-absorbing group having a pendant phenyl group or a silicon-silicon bond and cross-linked by acid or heat can be preferably used for 193nm exposure.

[0348] In addition, the present invention provides a pattern forming method, characterized in that, as a pattern forming method by a four-layer resist process using such a metal-containing film-forming composition, the method comprises the following steps: using the metal-containing film-forming composition to form a metal-containing film on a substrate to be processed, using a silicon-containing resist intermediate film material to form a silicon-containing resist intermediate film on the resist underlayer film, forming an organic antireflective film (BARC) or a bonding film on the silicon-containing resist intermediate film, and using a photoresist material to form a BARC or a bonding film. The method comprises the steps of: forming a resist upper film by forming a resist upper film, exposing the resist upper film to pattern exposure, developing the resist upper film with a developer to form a pattern on the resist upper film, using the resist upper film with the pattern as a mask, transferring the pattern to the BARC or the adhesion film and the silicon-containing resist intermediate film by dry etching, transferring the pattern to the metal-containing film by dry etching, using the silicon-containing resist intermediate film with the transferred pattern as a mask, processing the processed substrate to form a pattern on the processed substrate.

[0349] Furthermore, as a substitute for the silicon-containing resist intermediate film, an inorganic hard mask may be formed. In this case, at least, a metal-containing film is formed on a workpiece using the metal-containing film-forming composition of the present invention, an inorganic hard mask selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film is formed on the metal-containing film, a photoresist composition is used on the inorganic hard mask to form a resist upper film, a circuit pattern is formed on the resist upper film, the inorganic hard mask is etched using the patterned resist upper film as a mask, the metal-containing film is etched using the patterned inorganic hard mask as a mask, and then, the workpiece is etched using the patterned metal-containing film as a mask to form a pattern on the workpiece, thereby forming a circuit pattern of a semiconductor device on a substrate.

[0350] As described above, when an inorganic hard mask is formed on a metal-containing film, a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film (SiON film) can be formed by a CVD method, an ALD method, or the like. For example, the method for forming a silicon nitride film is described in Japanese Patent Application Publication No. 2002-334869 and International Publication No. 2004 / 066377. The film thickness of the inorganic hard mask is preferably 5 to 200 nm, and more preferably 10 to 100 nm. Furthermore, as an inorganic hard mask, a SiON film having a high effect as an anti-reflection film can be most preferably used. Since the substrate temperature when forming the SiON film becomes 300 to 500° C., the metal-containing film must withstand a temperature of 300 to 500° C. The metal-containing film-forming composition used in the present invention has high heat resistance and can withstand high temperatures of 300°C to 500°C, so a combination of an inorganic hard mask formed by CVD or ALD and a metal-containing film formed by spin coating is possible.

[0351] As described above, a photoresist film may be formed on an inorganic hard mask as a resist upper layer film, but an organic antireflection film (BARC) or a close contact film may be formed on the inorganic hard mask by spin coating, and then a photoresist film may be formed thereon. In particular, when a SiON film is used as an inorganic hard mask, the two-layer antireflection film of the SiON film and the BARC can suppress reflection even in immersion exposure with a high NA exceeding 1.0. Another advantage of forming a BARC is that it has the effect of reducing the tailing of the photoresist pattern on the SiON film.

[0352] In addition, in the present invention, as a pattern forming method by a multilayer resist process using such a metal-containing film-forming composition, a resist lower layer film is formed on a substrate to be processed, the metal-containing film-forming composition of the present invention is applied on the resist lower layer film, and then a metal-containing film is formed by heat treatment, and a resist upper layer film is formed on the metal-containing film using a photoresist material, and the resist upper layer film is pattern-exposed and then developed with a developer to form a pattern on the resist upper layer film, and the patterned resist upper layer film is used as a mask to transfer the pattern to the metal-containing film by dry etching, and the metal-containing film to which the pattern is transferred is used as a mask to transfer the pattern to the resist lower layer film by dry etching, and then the patterned resist lower layer film is used as a mask to process the substrate to form a pattern on the processed substrate, thereby forming a semiconductor device circuit pattern on the substrate.

[0353] As described above, a photoresist film may be formed on the metal-containing film as a resist upper layer film, but a contact film may be formed on the metal-containing film by spin coating and then a photoresist film may be formed thereon.

[0354] As described above, when forming the resist underlayer film on the processed substrate, the resist underlayer film can be formed by a method using a coating type organic underlayer film material, a CVD method, an ALD method, etc. As for the coating type organic underlayer film material, examples thereof include Japanese Patent Publication No. 2012-001687, Japanese Patent Publication No. 2012-077295, Japanese Patent Publication No. 2004-264710, Japanese Patent Publication No. 2005-043471, Japanese Patent Publication No. 2005-250434, Japanese Patent Publication No. 2007-293294, Japanese Patent Publication No. 200 8-065303, Japanese Patent Application Laid-Open No. 2004-205685, Japanese Patent Application Laid-Open No. 2007-171895, Japanese Patent Application Laid-Open No. 2009-014816, Japanese Patent Application Laid-Open No. 2007-199653, Japanese Patent Application Laid-Open No. 2008-274250, Japanese Patent Application Laid-Open No. 2010-122656, Japanese Patent Application Laid-Open No. 2012-2147 20, Japanese Patent Application Publication No. 2014-029435, International Publication No. 2012 / 077640, International Publication No. 2010 / 147155, International Publication No. 2012 / 077640, International Publication No. 2010 / 147155, International Publication No. 2012 / 176767, Japanese Patent Application Publication No. 2005-128509 ... The resins and compositions described in Japanese Patent Application No. 006-259249, Japanese Patent Application No. 2006-259482, Japanese Patent Application No. 2006-293298, Japanese Patent Application No. 2007-316282, Japanese Patent Application No. 2012-145897, Japanese Patent Application No. 2017-119671, and Japanese Patent Application No. 2019-044022.

[0355] The resist upper film in the above-mentioned multilayer resist process can be positive or negative, and can use the same photoresist composition as that commonly used. After the photoresist composition is spin-coated, it is pre-baked, preferably in the range of 60 to 180° C. and 10 to 300 seconds. Thereafter, it is exposed according to the general method, and then, post-exposure baking (PEB) and development are performed to obtain a resist pattern. In addition, the thickness of the resist upper film is not particularly limited, but 30 to 500 nm is more ideal, and 50 to 400 nm is particularly ideal.

[0356] Examples of the exposure light include high-energy rays having a wavelength of 300 nm or less, specifically, excimer lasers of 248 nm, 193 nm, and 157 nm, soft X-rays of 3 to 20 nm, electron beams, and X-rays.

[0357] The patterning method of the resist upper layer film is preferably performed by optical lithography with a wavelength of 5 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0358] In addition, it is preferable that the development method in the above-mentioned pattern forming method is set to development using an alkali or an organic solvent.

[0359] Next, the obtained resist pattern is used as a mask for etching. The etching of the silicon-containing resist intermediate film and the inorganic hard mask in the three-layer resist process is performed using a freon-based gas and the upper resist pattern as a mask. In this way, the silicon-containing resist intermediate film pattern and the inorganic hard mask pattern are formed.

[0360] Then, the obtained silicon-containing resist intermediate film pattern and inorganic hard mask pattern are used as masks to perform etching processing on the metal-containing film. The etching processing on the metal-containing film is preferably performed using an etching gas mainly containing a chlorine-based gas.

[0361] The subsequent etching of the workpiece can also be performed by a general method. For example, if the workpiece is a SiO2, SiN, or silicon dioxide-based low-k dielectric film, etching is performed using a Freon-based gas as the main component. When etching is performed using a Freon-based gas for substrate processing, the silicon-containing resist intermediate film pattern in the three-layer resist process is stripped off while the substrate is being processed.

[0362] The metal-containing film obtained by using the metal-containing film-forming composition of the present invention has a characteristic of being excellent in etching resistance when etching these workpieces.

[0363] In addition, the object to be processed (substrate to be processed) is not particularly limited, and is formed by using a substrate such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc., and forming a layer to be processed on the substrate. As for the layer to be processed, various Low-k films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, and barrier films thereof are used, and can be formed to a thickness of usually 50 to 10,000 nm, especially 100 to 5,000 nm. In addition, when forming the layer to be processed, the substrate and the layer to be processed may be made of different materials.

[0364] In the pattern forming method using the metal-containing film-forming composition of the present invention, it is more ideal to use a processed substrate having a structure or height difference of more than 30nm. As mentioned above, the metal-containing film-forming composition of the present invention has excellent filling / flattening properties, so even if there is a structure or height difference (concave and convex) with a height of more than 30nm on the processed substrate, a flat hardened film can still be formed. The height of the structure or height difference of the above-mentioned processed substrate is more ideally 30nm or more, more ideally 50nm or more, and more ideally 100nm or more. In the method of processing a substrate with a height difference having a pattern of the above height, by forming a film with the metal-containing film-forming composition of the present invention and filling / flattening, the film thickness of the resist intermediate film and the resist upper film formed later can be made uniform, so it becomes easy to ensure the exposure depth limit (DOF) during optical lithography, which is very ideal.

[0365] <Tone-reversal pattern forming method using a metal-containing film-forming composition>

[0366] The present invention also provides a tone-reversal pattern forming method, characterized in that, as a tone-reversal pattern forming method using such a metal-containing film-forming composition, the method comprises the following steps: forming a resist lower layer film on a substrate to be processed, forming a resist intermediate film, or a combination of an inorganic hard mask intermediate film selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film and an organic thin film on the resist lower layer film, forming a resist upper layer film on the resist intermediate film or the combination of the inorganic hard mask intermediate film and the organic thin film using a photoresist material, exposing the resist upper layer film to a pattern, and then developing the resist upper layer film with a developer to form a pattern on the resist upper layer film, using the resist upper layer film with the pattern formed as a mask, transferring the pattern to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film by dry etching, and then etching the resist intermediate film with the transferred pattern. , or an inorganic hard mask intermediate film as a mask, and transferring the pattern to the resist underlayer film by dry etching; on the resist underlayer film having the pattern formed, the metal-containing film is covered with the above-mentioned metal-containing film forming composition, and the space between the resist underlayer film patterns is filled with the metal-containing film; the metal-containing film covered on the resist underlayer film having the pattern is etched back by a chemical stripper or dry etching to expose the top surface of the resist underlayer film having the pattern; the resist intermediate film or the hard mask intermediate film remaining on the top surface of the resist underlayer film is removed by dry etching; the resist underlayer film having the pattern formed on the surface exposed is removed by dry etching; a reverse pattern of the original pattern is formed on the metal-containing film; the metal-containing film having the reverse pattern formed is used as a mask, and the processed substrate is processed to form a reverse pattern on the processed substrate.

[0367] For an example of the formation of a tone reversal pattern, if Figure 2 The specific expression is as follows. Figure 2 As shown in (G), after a resist lower layer film 7 composed of a coating type organic lower layer film material is formed on the processed layer 2 stacked on the processed substrate 1, a silicon-containing resist intermediate film 4 is formed, and a resist upper layer film 5 is formed thereon.

[0368] Then, if Figure 2 As shown in (H), the used portion (exposed portion) 6 of the resist upper film 5 is exposed, PEB and development are performed to form a resist upper film pattern 5a ( Figure 2 (I)). Using the obtained resist upper film pattern 5a as a mask, the silicon-containing resist intermediate film 4 is etched using CF-based gas to form a silicon-containing resist intermediate film pattern 4a ( Figure 2 After the resist upper film pattern 5a is removed, the obtained silicon-containing resist intermediate film pattern 4a is used as a mask to perform oxygen plasma etching on the resist lower film 7 composed of the coating type organic lower film material to form a resist lower film pattern 7a composed of the coating type organic lower film material ( Figure 2 (K)).

[0369] After coating the metal-containing film-forming composition of the present invention on the resist underlayer film pattern 7a composed of the coating type organic underlayer film material, the metal-containing film 8 is covered by heat treatment, and the space between the resist underlayer film patterns 7a composed of the coating type organic underlayer film material is filled with the metal-containing film ( Figure 2 Then, the metal-containing film 8 covering the resist lower film pattern 7a composed of the coating type organic lower film material is etched back by chemical stripping agent or dry etching to expose the top surface of the resist lower film pattern 7a composed of the coating type organic lower film material ( Figure 2 Then, the silicon-containing resist intermediate film pattern 4a remaining on the top surface of the resist lower film pattern 7a composed of the coating type organic lower film material is removed by dry etching ( Figure 2 (N)). Then, the resist lower film pattern 7a composed of the coating type organic lower film material is removed by dry etching, and a reverse pattern of the original pattern is formed on the metal-containing film (forming a metal-containing film pattern 8a formed by reversing the resist lower film pattern) ( Figure 2 After that, the metal-containing film pattern 8a obtained by inverting the resist lower film pattern is used as a mask and the processed substrate is processed to form a tone inversion pattern ( Figure 2 (P)).

[0370] As described above, when forming the resist underlayer film on the processed substrate, the resist underlayer film can be formed by a method using a coating type organic underlayer film material, a CVD method, an ALD method, etc. As for the coating type organic underlayer film material, examples thereof include Japanese Patent Publication No. 2012-1687, Japanese Patent Publication No. 2012-77295, Japanese Patent Publication No. 2004-264710, Japanese Patent Publication No. 2005-043471, Japanese Patent Publication No. 2005-250434, Japanese Patent Publication No. 2007-293294, Japanese Patent Publication No. 2008-653 03, Japanese Patent Publication No. 2004-205685, Japanese Patent Publication No. 2007-171895, Japanese Patent Publication No. 2009-14816, Japanese Patent Publication No. 2007-199653, Japanese Patent Publication No. 2008-274250, Japanese Patent Publication No. 2010-122656, Japanese Patent Publication No. 2012-214720, Japanese Patent Publication No. International Publication No. WO2014-29435, International Publication No. WO2012 / 077640, International Publication No. WO2010 / 147155, International Publication No. WO2012 / 077640, International Publication No. WO2010 / 147155, International Publication No. WO2012 / 176767, Japanese Patent Application Laid-Open No. 2005-128509, Japanese Resins and compositions described in Japanese Patent Application Laid-Open Nos. 2006-259249, 2006-259482, 2006-293298, 2007-316282, 2012-145897, 2017-119671, and 2019-44022.

[0371] In the above tone reversal pattern forming method, after coating the obtained resist underlayer film pattern with a metal-containing film-forming composition, it is preferable to remove the metal-containing film using a dry etching gas mainly composed of a chlorine-based gas in order to expose the top surface of the resist underlayer film pattern. Thereafter, the resist intermediate film or hard mask intermediate film remaining on the above resist underlayer film is removed by dry etching using a freon-based gas, and the exposed resist underlayer film pattern is removed by dry etching using an oxygen-based gas to form a metal-containing film pattern.

[0372] In the above-mentioned tonality reversal pattern forming method, it is more ideal that the resist lower film pattern has a structure or height difference of more than 30nm. As mentioned above, the metal-containing film forming composition of the present invention has excellent filling / planarization characteristics, so even if the processed film has a structure or height difference (concave and convex) of more than 30nm, a flat hardened film can still be formed. It is more ideal that the height of the structure or height difference of the above-mentioned resist lower film pattern is more than 30nm, more ideally more than 50nm, and even more ideally more than 100nm. In the method of reversing the resist lower film pattern having the above-mentioned height pattern, by forming a film of the metal-containing film forming composition of the present invention and performing filling / planarization, the pattern can be reversed / transferred with high precision, so it is very ideal. Compared with the resist underlayer film using the known coating type organic underlayer material, the dry etching resistance using Freon-based gas is excellent, so by reversing the resist underlayer film pattern with the above-mentioned metal-containing film forming composition, the desired resist pattern can be formed on the processed film with high precision.

[0373] [Example]

[0374] Hereinafter, the present invention will be described in more detail by showing synthesis examples, comparative synthesis examples, embodiments, and comparative examples, but the present invention is not limited thereto. In addition, as for molecular weight and dispersity, the weight average molecular weight (Mw) and number average molecular weight (Mn) calculated as polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent were obtained to obtain dispersity (Mw / Mn).

[0375] [Synthesis example]

[0376] In the following synthesis examples and comparative examples, the following tin compounds Sn: (Sn-1) to (Sn-3), raw material group W: (W1) to (W10), and raw material group G: (G-1) to (G-12) were used. Each raw material group is shown below.

[0377] Tin compounds Sn:

[0378] [Chemistry 52]

[0379]

[0380] Raw material group W:

[0381] [Chemistry 53]

[0382]

[0383] Raw material group G:

[0384] [Chemistry 54]

[0385]

[0386] [Synthesis Example 1] Synthesis of Metal-Containing Film-Forming Compound (A-1)

[0387] 5.0 g of the tin compound (Sn-1), 4.6 g of the raw material (W1) and 100 g of toluene were added, and the mixture was reacted for 7 hours at 100° C. while removing tert-butyl alcohol. After the reaction, the solvent was removed under reduced pressure to obtain a compound (A-1).

[0388] (A-1): Mw=322, Mw / Mn=1.05

[0389] [Synthesis Example 2] Synthesis of Metal-Containing Film-Forming Compound (A-2)

[0390] 5.0 g of the tin compound (Sn-3), 6.0 g of the raw material (W2) and 100 g of toluene were added and reacted at 100° C. for 7 hours. After the reaction, the solvent was removed under reduced pressure to obtain a compound (A-2).

[0391] (A-2): Mw=344, Mw / Mn=1.08

[0392] [Synthesis Example 3] Synthesis of Metal-Containing Film-Forming Compound (A-3)

[0393] 5.0 g of a tin compound (Sn-2), 6.8 g of a raw material (W3) and 100 g of toluene were added, and the mixture was reacted for 7 hours at 130° C. while removing water. After the reaction, the solvent was removed under reduced pressure to obtain a compound (A-3).

[0394] (A-3): Mw=356, Mw / Mn=1.07

[0395] [Synthesis Example 4] Synthesis of Metal-Containing Film-Forming Compound (A-4)

[0396] 5.0 g of the tin compound (Sn-3), 6.0 g of the raw material (W2), 1.3 g of the raw material (G-1) and 100 g of toluene were added and reacted at 100° C. for 7 hours. After the reaction, the solvent was removed under reduced pressure to obtain a compound (A-4).

[0397] (A-4): Mw=401, Mw / Mn=1.24

[0398] [Synthesis Examples 5 to 12] Synthesis of Metal-Containing Film-Forming Compounds (A-5) to (A-12)

[0399] The above raw material W and the above raw material group G were used in the feed amounts shown in Tables 1-1 to 1-2, and (A-5) to (A-12) were obtained under the same reaction conditions as in Synthesis Example 4. In addition, - indicates that the raw material group was not used. The weight average molecular weight (Mw) and dispersity (Mw / Mn) of these compounds were obtained. The results are shown in Table 3.

[0400] [Table 1-1]

[0401]

[0402]

[0403] [Table 1-2]

[0404]

[0405]

[0406] [Comparative Synthesis Example 1] Synthesis of Metal-Containing Film-Forming Compound (R-1) for Comparative Example

[0407] 5.0 g of the tin compound (Sn-3) was stirred at room temperature, and 5.0 g of the raw material (G-10) was added dropwise. After the addition, the temperature was raised to 80°C and stirred for 7 hours. After the reaction was completed, the acrylic acid was removed under reduced pressure to obtain (R-1).

[0408] [Comparative Synthesis Example 2] Synthesis of Metal-Containing Film-Forming Compound (R-2) for Comparative Example

[0409] 5.0 g of the tin compound (Sn-2), 6.0 g of the raw material (G-11) and 100 g of toluene were added, and the mixture was reacted for 7 hours at 130° C. while removing water. After the reaction, the solvent was removed under reduced pressure to obtain (R-2).

[0410] [Comparative Synthesis Example 3] Synthesis of Metal-Containing Film-Forming Compound (R-3) for Comparative Example

[0411] 5.0 g of the tin compound (Sn-2), 11.4 g of the raw material (G-12), and 100 g of toluene were added, and the mixture was reacted for 7 hours at 130° C. while removing water. After the reaction, the solvent was removed under reduced pressure to obtain (R-3).

[0412] The feed amounts and the synthesized compounds of Comparative Synthesis Examples 1 to 3 are shown in Table 2. The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) of these compounds were determined. The results are shown in Table 3.

[0413] [Table 2]

[0414]

[0415] [Table 3]

[0416]

[0417]

[0418] [Synthesis of Metal-Containing Film-Forming Compound (R-4) for Comparative Example]

[0419] As a compound having a metal other than the metal-containing film-forming compound of the present invention, a titanium compound reported in [Synthesis Example A-II] of Japanese Patent No. 6189758 was synthesized.

[0420] While stirring a solution of 284 g of titanium tetraisopropoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) in IPA500 g, a solution of 27 g of deionized water in IPA500 g was added dropwise at room temperature over 2 hours. 120 g of 2-methyl-2,4-pentanediol was added to the obtained solution, and the mixture was stirred at room temperature for 30 minutes. After concentrating the solution at 30°C under reduced pressure, the solution was heated to 60°C and continued to be heated under reduced pressure until no distillate appeared. When no distillate was seen, 1,200 g of PGMEA was added and heated at 40°C under reduced pressure until no IPA distilled out, to obtain 1,000 g of PGMEA solution of titanium-containing compound (R-4) (compound concentration 20 mass %). The polystyrene-equivalent molecular weight thereof was measured, and Mw=1,100.

[0421] [Synthesis of Organic Film-Forming Resin (R-5) for Comparative Example]

[0422] Under 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. After that, the homogenized mixed solution of 8.0 g of p-toluenesulfonic acid monohydrate and 8.0 g of PGME was slowly added dropwise, and the reaction was carried out at an internal temperature of 80°C for 8 hours. After the reaction was terminated, it was cooled to room temperature, 2,000 ml of MIBK was added, and it was washed 6 times with 500 ml of pure water, and the organic layer was dried under reduced pressure. After adding 300 g of THF to the residue to make a uniform solution, it was crystallized in 2,000 g of hexane. The precipitated crystals were separated by filtration, washed twice with 500 g of hexane, and recovered. The recovered crystals were vacuum dried at 70°C to obtain resin (R-5).

[0423] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC. The results are as follows.

[0424] (R-5): Mw=3,300, Mw / Mn=2.54

[0425] [Chemistry 55]

[0426]

[0427] Examples 1-1 to 1-19, Comparative Examples 1-1 to 1-5

[0428] The metal-containing film-forming compositions UDL-1 to -16 used in Examples 1-1 to 1-19 and the metal-containing film-forming compositions (Comparative Examples UDL-1 to -5) used in Comparative Examples 1-1 to 1-4 were prepared as follows.

[0429] [Metal-containing film-forming composition UDL-1]

[0430] The metal-containing film-forming compound (A-1) was dissolved in a mixed solvent of 0.5 mass % of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (CyHO) containing a surfactant FC-4430 (manufactured by Sumitomo 3M Co., Ltd.) at the ratio shown in Table 4, and filtered with a 0.2 μm membrane filter to prepare a metal-containing film-forming composition (UDL-1).

[0431] [Preparation of Metal-Containing Film-Forming Compositions (UDL-2 to 16) and Metal-Containing Film-Forming Compositions for Comparative Examples (Comparative Examples UDL-1 to 5)]

[0432] Each solution was prepared in the same manner as UDL-1 except that the type and content of each component were set as shown in Table 4. In Table 4, "-" indicates that the component was not used. The following formula (C-1) was used as the crosslinking agent, 1,6-diacetoxyhexane (boiling point 260° C.) was used as the high boiling point solvent (D-1), a polymer for fluidity promoter (F-1) was used, and the thermal acid generator (TAG) was the formula (TAG-1) described later.

[0433] [Crosslinking agent]

[0434] The cross-linking agent (C-1) used in the metal-containing film-forming composition is shown below.

[0435] [Chemistry 56]

[0436]

[0437] [Synthesis Example of Fluidity Improver Polymer] Synthesis of Fluidity Improver Polymer (F-1)

[0438] Under nitrogen atmosphere, 20.0 g of cresol novolac, 27.6 g of potassium carbonate and 100 g of DMF were added to prepare a uniform dispersion at an internal temperature of 50°C. 11.9 g of propargyl bromide was slowly added and the reaction was carried out at an internal temperature of 50°C for 24 hours. 300 ml of methyl isobutyl ketone and 300 g of pure water were added to the reaction solution to dissolve the precipitated salt, and the separated water layer was removed. The organic layer was then washed 6 times with 100 g of 3% nitric acid aqueous solution and 100 g of pure water, and then the organic layer was dried under reduced pressure to obtain resin (F-1).

[0439] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC. The results are as follows.

[0440] (F-1): Mw=8,500, Mw / Mn=3.46

[0441] [Chemistry 57]

[0442]

[0443] [Thermal acid generator]

[0444] The thermal acid generator (TAG-1) used in the metal-containing film-forming composition is shown below.

[0445] [Chemistry 58]

[0446]

[0447] [Table 4]

[0448]

[0449] As shown in Table 4, the metal-containing film-forming composition of the present invention (Examples 1-1 to 1-12) can be prepared with a composition containing PGMEA, and compared with the comparative example UDL-2 in which two styrene carboxylic acids are bonded, which cannot be prepared with a composition containing PGMEA, it is confirmed that the solvent solubility is excellent. In addition, UDL-4 to UDL-12 obtained by reacting raw material group W and raw material group G can be prepared with a composition of PGMEA alone, and the solvent solubility is also excellent. It is believed that this is due to the collapse of the symmetry of the molecule.

[0450] [Evaluation of heat resistance and solvent resistance]

[0451] The metal-containing film-forming composition (UDL-1 to 16, comparative example UDL-1 to 5) prepared above was applied on a silicon substrate, and after calcining at 100° C. for 60 seconds, the film thickness (a [nm]) was measured. Then, after calcining at each baking temperature shown in Table 5 for 60 seconds, the film thickness (b [nm]) was measured, and the difference in film thickness before and after the additional baking treatment was calculated (residual film ratio: (b / a)×100).

[0452] Then, a PGMEA solvent was placed on it, left to stand and spin-dried within 30 seconds, and baked at 100°C for 60 seconds to evaporate PGMEA, and the film thickness (c [nm]) was measured. The film thickness difference before and after PGMEA treatment was calculated (residual film ratio: (c / b) × 100). The results are shown in Table 5 below.

[0453] [Table 5]

[0454]

[0455] As shown in Table 5, the residual film rate ((b / a)×100) of the metal-containing film-forming composition of the present invention (Examples 1-1 to 1-12) after high-temperature additional baking treatment is 55% or more, and it can be understood that the film has the required high-temperature baking resistance in the resist underlayer film. On the other hand, the residual film rate ((b / a)×100) of Comparative Example 1-3, which does not have a catechol·diol structure, after high-temperature additional baking treatment is 43%, confirming that its heat resistance is poor. In addition, if Examples 1-17 to 1-19 and Comparative Example 1-4, which were subjected to high-temperature additional baking at 350°C, are compared, it is confirmed that Comparative Example 1-4 is a state where the residual film rate is 8% and the film is almost not left, but Examples 1-17 to 1-19 are 35%, 38%, 39% and 30% or more respectively, and the film still remains, which can be understood that it has heat resistance that allows film formation even under ultra-high temperature baking conditions of 350°C. This is believed to be because the compound of the present invention is bonded to tin at two locations with an organic ligand like a chelate. Then, the film subjected to high-temperature additional baking treatment had a residual film rate ((c / b)×100) of 99% or more after PGMEA rinsing treatment, which shows that a crosslinking reaction has occurred and exhibits sufficient solvent resistance. UDL-15 to which a crosslinking agent (C-1) was added had a residual film rate after baking increased from 61% to 65% compared to UDL-11 to which no crosslinking agent (C-1) was added. This is believed to be the result of crosslinking effectively occurring due to the crosslinking agent, and sublimation products being suppressed. Furthermore, when comparing UDL-4 and UDL-13 to which a thermal acid generator (TAG-1) is added, the residual film rate ((c / b)×100) after PGMEA rinsing treatment after baking at 250°C for UDL-4 is 99.7%, while the residual film rate ((c / b)×100) after baking at 200°C and PGMEA rinsing treatment for UDL-13 is 100%, which is a result of increased curability. This is believed to be the result of the effective occurrence of the cross-linking reaction caused by the detachment of the leaving group due to the addition of the thermal acid generator. On the other hand, the residual film rate ((b / a)×100) after the high-temperature additional baking treatment of the comparative examples UDL-1 and UDL-2 is less than 5%. This is believed to be the result of the fact that although there are cross-linking groups, the molecules are decomposed and sublimated before the cross-linking reaction occurs due to insufficient heat resistance.

[0456] In addition, regarding the metal-containing compound different from the metal-containing film-forming compound of the present invention, Comparative Examples 1-4 using the titanium compound reported in [Synthesis Example A-II] of Japanese Patent Gazette No. 6189758 showed sufficient solvent resistance, but the difference in film thickness before and after high-temperature additional baking treatment was large. It can be understood that the volume shrinkage caused by high-temperature baking is large compared to the metal-containing film-forming compound of the present invention.

[0457] Examples 2-1 to 2-16, Comparative Examples 2-1 to 2-3

[0458] [Landfill characteristics evaluation]

[0459] The above-mentioned metal-containing film-forming compositions (UDL-1 to 16 and comparative examples UDL-3 to 5) having good film-forming properties after solvent resistance evaluation and additional baking were coated on SiO2 wafer substrates having dense line and space patterns (line width 40nm, line depth 120nm, and the distance between the centers of two adjacent lines is 80nm), and heated for 60 seconds at the temperature shown in Table 6 using a hot plate to form a metal-containing film with a film thickness of 100nm. The substrate used was as follows Figure 3 The base substrate 9 (SiO2 wafer substrate) having a dense line and space pattern as shown in (Q) (bird's-eye view) and (R) (cross-sectional view). The cross-sectional shape of each wafer substrate obtained was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. to confirm whether the uneven substrate could be buried. The results are shown in Table 6. When a metal-containing film-forming composition with poor filling characteristics was used, the uneven substrate could not be buried well in this evaluation. When a metal-containing film-forming composition with good filling characteristics was used, in this evaluation, Figure 3 As shown in (S), the lines of the base substrate 9 having a dense line and space pattern can be filled without gaps with the metal-containing film 10. ○ means that it can be filled without large voids, △ means that voids are visually observed, and × means that it cannot be filled.

[0460] [Table 6]

[0461]

[0462]

[0463] As shown in Table 6, in Examples 2-1 to 2-16 using the metal-containing film-forming composition of the present invention (UDL-1 to 16), it was confirmed that dense line and space patterns can be filled without voids, and good filling characteristics are obtained. On the other hand, in Comparative Example 2-2 using the titanium compound reported in [Synthesis Example A-II] of Japanese Patent Gazette No. 6189758, voids were observed at the bottom of the pattern. As observed in the above-mentioned solvent resistance evaluation, it is speculated that voids occur because of the large volume shrinkage caused by high-temperature baking.

[0464] Examples 3-1 to 3-16, Comparative Examples 3-1 to 3-3

[0465] [Planarization characteristics evaluation]

[0466] For example Figure 4 The base substrate 11 (SiO2 wafer substrate) having a dense line and space pattern shown in (T) is as follows: Figure 4 The cross-sectional shape of each wafer substrate obtained in the above-mentioned embedding characteristic evaluation is generally observed using a scanning electron microscope (SEM), and the height difference ( Figure 4 The results are shown in Table 7. In this evaluation, the smaller the height difference is, the better the planarization characteristics are.

[0467] [Table 7]

[0468]

[0469]

[0470] As shown in Table 7, Examples 3-1 to 3-16 using the metal-containing film-forming composition (UDL-1 to 16) of the present invention have been confirmed to have a small height difference between the patterned portion and the non-patterned portion of the film and excellent planarization characteristics compared to Comparative Example 3-2 using the titanium compound reported in [Synthesis Example A-II] of Japanese Patent Gazette No. 6189758 and Comparative Example 3-3 using an organic resist underlayer film material. It was also confirmed that the planarity was excellent compared to Comparative Example 3-1 using a similar tin-containing compound. It is believed that this is because the compound of the present invention has an asymmetric structure and contributes to the improvement of thermal fluidity.

[0471] In addition, Examples 3-14 and 3-16 to which a high boiling point solvent (D-1) and a fluidity enhancer (F-1) were added showed excellent planarization characteristics compared to Examples 3-4 and 3-11 to which these were not added. It can be understood that the use of a high boiling point solvent (D-1) and a fluidity enhancer (F-1) can further improve the thermal fluidity of the metal-containing film-forming compound.

[0472] Examples 4-1 to 4-3, Comparative Examples 4-1 to 4-3

[0473] [Evaluation of etching resistance]

[0474] The metal-containing film-forming composition (UDL-3, UDL-7 and UDL-9, comparative examples UDL-3 to 5) having good film-forming properties after additional baking in the above solvent resistance evaluation was applied on a silicon substrate, and heated for 60 seconds at the temperature shown in Table 8 using a hot plate to form a metal-containing film with a thickness of 200 nm. An etching test was performed using CF-based gas and O2-based gas under the following conditions to obtain the difference in film thickness of the organic film before and after etching. The results are shown in Table 8. In addition, a dry etching device TE-8500 manufactured by Tokyo Electron Co., Ltd. was used for etching.

[0475] The CF4-based gas etching conditions are as follows.

[0476]

[0477] The O2-based gas etching conditions are as follows.

[0478]

[0479] [Table 8]

[0480]

[0481] As shown in Table 8, it can be understood that Examples 4-1 to 4-3 using the metal-containing film-forming composition for resist (UDL-3, 7, 9) of the present invention, Comparative Example 4-1 using a similar metal-containing film-forming composition (Comparative Example UDL-3), and Comparative Example 4-2 using a titanium compound (Comparative Example UDL-4) show excellent etching resistance to CF-based gases, and O2 etching resistance is even better, compared with Comparative Example 4-3 using Comparative Example UDL-5 using an organic resist underlayer film material.

[0482] [Pattern Formation Method (Examples 5-1 to 5-3, Comparative Examples 5-1 to 5-2)]

[0483] The metal-containing film-forming compositions (UDL-3, UDL-7 and UDL-9, comparative examples UDL-4 to 5) with good film-forming properties after additional baking in the above solvent resistance evaluation were respectively coated on SiO2 wafer substrates with a groove pattern (groove width 10μm, groove depth 0.10μm), and calcined at 250°C for 60 seconds in the atmosphere to form a metal-containing film with a thickness of 100nm. A silicon-containing resist intermediate layer material (SOG-1) was coated thereon and baked at 220°C for 60 seconds to form a resist intermediate layer film with a thickness of 30nm, and an ArF single-layer resist for the resist upper layer film material was coated thereon and baked at 105°C for 60 seconds to form a photoresist film with a thickness of 100nm. A wet protection film material (TC-1) was coated on the photoresist film and baked at 90°C for 60 seconds to form a protective film with a thickness of 50nm.

[0484] A polymer represented by an ArF silicon-containing intermediate film polymer (SiP1) as a silicon-containing anti-etching intermediate layer material (SOG-1) and a cross-linking catalyst (CAT1) are dissolved in an organic solvent containing 0.1 mass % of FC-4430 (manufactured by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 9, and filtered through a filter material made of fluororesin with a pore size of 0.1 μm to prepare a silicon-containing anti-etching intermediate layer material (SOG-1).

[0485] [Table 9]

[0486]

[0487] The structural formulas of the ArF silicon-containing interlayer polymer (SiP1) and the crosslinking catalyst (CAT1) used are shown below.

[0488] [Chemistry 59]

[0489]

[0490] As for the resist upper layer film material (single-layer resist for ArF), a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) are dissolved in a solvent containing 0.1 mass % of a surfactant FC-4430 (manufactured by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 10, and the mixture is prepared by filtering through a filter material made of a 0.1 μm fluororesin.

[0491] [Table 10]

[0492]

[0493] The polymer (RP1), the acid generator (PAG1), and the basic compound (Amine1) used in the resist upper layer film material (ArF single-layer resist) are shown below.

[0494] [Chemistry 60]

[0495]

[0496] The wet protective film material (TC-1) was prepared by dissolving the protective film polymer (PP1) in an organic solvent at the ratio shown in Table 11 and filtering through a 0.1 μm fluororesin filter.

[0497] [Table 11]

[0498]

[0499] The polymer (PP1) used for the wet protective film material (TC-1) is shown below.

[0500] [Chemistry 61]

[0501]

[0502] Then, exposure was performed using an ArF immersion exposure device (manufactured by Nikon Co., Ltd.; NSR-S610C, NA1.30, σ0.98 / 0.65, 35 degree dipole s-polarized illumination, 6% half-step phase shift mask), baked (PEB) at 100°C for 60 seconds, and developed with a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain a 55nm1:1 positive straight line and space pattern (resist pattern).

[0503] Then, by dry etching, the resist pattern is used as a mask to etch the silicon-containing resist intermediate layer material (SOG-1) to form a hard mask pattern, the obtained hard mask pattern is used as a mask to etch the metal oxide film to form a metal oxide film pattern, and the obtained metal oxide film pattern is used as a mask to etch the SiO2 film. The etching device used is ULVAC CE-3001, and the etching conditions are as follows.

[0504] Transfer conditions of the resist pattern to the silicon-containing resist intermediate layer material (SOG-1).

[0505] Dry etching conditions using CF4 gas

[0506] Pressure: 1Pa

[0507] Antenna RF power: 100W

[0508] Bias RF energy: 15W

[0509] CF4 gas flow rate: 15sccm

[0510] Time: 60 seconds

[0511] Transfer conditions of SOG-1 hard mask pattern to metal-containing film.

[0512] Pressure: 1Pa

[0513] Antenna RF energy: 320W

[0514] Bias RF energy: 30W

[0515] Cl2 gas flow rate: 25sccm

[0516] Time (Example 5-1 to Example 5-3): 15 sec

[0517] Time (Comparative Example 5-1 and Comparative Example 5-2): 60 sec

[0518] Transfer conditions of metal-containing film patterns to SiO2 films.

[0519] Dry etching conditions using CF4 gas

[0520] Pressure: 1Pa

[0521] Antenna RF power: 100W

[0522] Bias RF energy: 15W

[0523] CF4 gas flow rate: 15sccm

[0524] Time: 60 seconds

[0525] Table 12 shows the results of observing the pattern cross section with an electron microscope (S-4700) manufactured by Hitachi, Ltd.

[0526] [Table 12]

[0527]

[0528] As shown in Table 12, in Examples 5-1 to 5-3 using the metal oxide film forming composition (UDL-3, 7, 9) of the present invention, the resist upper film pattern is finally well transferred to the substrate, confirming that the metal oxide film forming composition of the present invention can be ideally used in the micro-processing of the multilayer resist method. On the other hand, Comparative Example 5-1, which was confirmed to have insufficient performance in the evaluation of the embedding characteristics and the evaluation of the flattening characteristics, had pattern collapse during pattern processing, and ultimately failed to obtain a good pattern. In addition, although there were no problems in the evaluation of the embedding characteristics and the flattening characteristics, Comparative Example 5-2, which was confirmed to have insufficient performance in the evaluation of the dry etching resistance, had wrinkles in the pattern shape during pattern processing, and ultimately failed to obtain a good pattern.

[0529] According to the above, since the metal oxide film forming compound of the present invention is an organic tin compound that takes into account both thermal fluidity and thermal curing properties to a high degree, the metal-containing film forming composition using it can provide a metal-containing film such as a resist underlayer film material that has excellent dry etching resistance relative to known organic underlayer film materials and has a high degree of filling / planarization properties. It 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.

[0530] This manual contains the following aspects.

[0531] [1]: A metal-containing compound for film formation, characterized in that:

[0532] The compound is represented by the following general formula (M):

[0533] [Chemistry 62]

[0534]

[0535] In the general formula (M), R1 and R2 are each independently an organic group or a halogen atom, and W is a divalent organic group represented by the following general formula (W-1) or (W-2);

[0536] [Chemistry 63]

[0537]

[0538] In the general formula (W-1), l is an integer of 2 to 3, R3 and R4 are each independently a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, a hydrogen atom, or a halogen atom, or R3 and R4 on the same carbon atom together with the carbon atom to which they are bonded form a carbonyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the alkoxy group may also have an ester group or an amide group; and R3 and R4 on the same carbon atom may also be bonded to To form a ring structure, R3 and R4 on adjacent carbons may also be bonded to form a ring structure; in the general formula (W-2), R5 is each independently a substituted or unsubstituted straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, or a halogen atom, the alkyl group, the alkenyl group, the alkynyl group, and the alkoxy group may also have an ester group or an amide group, n is an integer of 0 to 1, m is an integer of 0 to 6, and * is a bonding site with -OSn.

[0539] [2]: A metal-containing film-forming compound as described in [1], wherein in the general formula (M), R1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated 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, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms.

[0540] [3]: The metal-containing film-forming compound according to [1] or [2], wherein R2 is -OC(=O)R2', wherein R2' is a monovalent organic group.

[0541] [4]: The metal-containing film-forming compound of [3], wherein R2′ is any of the following general formulas (A-1) to (A-4) or the following general formula (2) or the following general formula (3);

[0542] [Chemistry 64]

[0543]

[0544] In the general formulas (A-1) to (A-4), Y A1 , Y A2may be the same as or different from each other, and are a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms; R A is a hydrogen atom, a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms, R A1 It is an organic group represented by the following general formula (1) in which the protecting group is released by the action of one or both of acid and heat to generate one or more hydroxyl groups or carboxyl groups, and * represents the bonding site with the carbonyl group;

[0545] [Chemistry 65]

[0546]

[0547] In the general formula (1), R A2 is an organic group whose protecting group will be removed by the action of one or both of acid and heat, and * indicates A1 or Y A2 The bond of

[0548] [Chemistry 66]

[0549]

[0550] In the general formula (2), X is a divalent organic group having 1 to 31 carbon atoms, B is the following general formula (B), and * indicates the bonding site with the carbonyl group;

[0551] [Chemistry 67]

[0552] B=*-Y B -R B (B)

[0553] In the general formula (B), Y B is a substituted or unsubstituted saturated or unsaturated divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted divalent aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted divalent aralkyl group having 7 to 31 carbon atoms, and may be bonded to an adjacent group via an oxygen atom or an NH group, R B is a hydroxyl group or any one of the structures represented by the following general formulas (B-1) to (B-3); * represents the bonding site with the carbonyl group;

[0554] [Chemistry 68]

[0555]

[0556] In the general formulas (B-1) to (B-3), R B1is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents B The bond of

[0557] [Chemistry 69]

[0558]

[0559] In the general formula (3), X is a divalent organic group having 1 to 31 carbon atoms, C is a group represented by the following general formulas (C-1) to (C-4), and * represents the bonding site to the carbonyl group;

[0560] [Chemistry 70]

[0561]

[0562] In the general formulas (C-1) and (C-3), R C1 are each independently a hydrogen atom or a methyl group, and they may be the same or different from each other in the same formula; in (C-3) to (C-4), R C2 It is a hydrogen atom, or a substituted or unsubstituted saturated or unsaturated monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms; * indicates the bonding site to the carbonyl group.

[0563] [5]: The metal-containing film-forming compound according to [4], wherein Y in the general formula (A-1) to (A-4) A1 , X in the general formula (2) or X in the general formula (3) is a substituted or unsubstituted unsaturated hydrocarbon having 2 to 20 carbon atoms.

[0564] [6]: The metal-containing film-forming compound according to [4] or [5], wherein Y in the general formula (A-1) to (A-4) A1 , X in the general formula (2), or X in the general formula (3) is the following general formula (4);

[0565] [Chemistry 71]

[0566]

[0567] In the general formula (4), R a , R b and R C is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, R a and R b They may also be bonded to form a cyclic substituent; *1 and *2 represent the bonding sites with the carbonyl group, respectively, and the substitution positions of *1 and *2 may also be interchangeable.

[0568] [7]: A metal-containing film-forming compound as described in any one of [1] to [6], wherein the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn of the metal-containing film-forming compound in terms of polystyrene as measured by gel permeation chromatography is 1.00≤Mw / Mn≤1.50.

[0569] [8]: A metal-containing film-forming composition that functions as a resist underlayer film material used in semiconductor manufacturing, characterized in that:

[0570] Contains (a) the metal-containing film-forming compound according to any one of [1] to [7] and (b) an organic solvent.

[0571] [9]: The metal-containing film-forming composition of [8] can be used as a resist underlayer film used in a multilayer resist method, and further contains one or more of (c) a cross-linking agent, (d) a surfactant, (e) a fluidity promoter, and (f) an acid generator.

[0572]

[10] : The metal-containing film-forming composition of [8] or [9], wherein the (b) organic solvent is a mixture of one or more organic solvents having a boiling point of less than 180°C and one or more organic solvents having a boiling point of 180°C or more.

[0573]

[11] : A pattern forming method is a method for forming a pattern on a processed substrate, characterized by comprising the following steps:

[0574] (I-1) a step of coating a metal-containing film-forming composition as described in any one of [8] to

[10] on a substrate to be processed, and then performing a heat treatment to form a metal-containing film;

[0575] (I-2) forming a resist upper layer film on the metal-containing film using a photoresist material;

[0576] (I-3) exposing the resist upper layer film to pattern exposure and then developing the film with a developer to form a pattern on the resist upper layer film;

[0577] (I-4) a step of transferring the pattern to the metal-containing film by dry etching using the patterned resist upper layer film as a mask; and

[0578] (I-5) A step of processing the substrate to be processed by using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0579]

[12] : A method for forming a pattern on a substrate to be processed, characterized by comprising the following steps:

[0580] (II-1) a step of coating a metal-containing film-forming composition as described in any one of [8] to

[10] on a substrate to be processed, and then performing a heat treatment to form a metal-containing film;

[0581] (II-2) a step of forming a resist intermediate film on the metal-containing film;

[0582] (II-3) forming a resist upper film on the resist intermediate film using a photoresist material;

[0583] (II-4) exposing the resist upper layer film to pattern exposure and then developing the film with a developer to form a pattern on the resist upper layer film;

[0584] (II-5) a step of transferring the pattern to the resist intermediate film by dry etching using the patterned resist upper layer film as a mask;

[0585] (II-6) a step of transferring the pattern to the metal-containing film by dry etching using the resist intermediate film to which the pattern has been transferred as a mask; and

[0586] (II-7) A step of processing the substrate to be processed by using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0587]

[13] : A method for forming a pattern on a substrate to be processed, characterized by comprising the following steps:

[0588] (III-1) a step of coating a metal-containing film-forming composition as described in any one of [8] to

[10] on a substrate to be processed, and then performing a heat treatment to form a metal-containing film;

[0589] (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film on the metal-containing film;

[0590] (III-3) forming an organic thin film on the inorganic hard mask intermediate film;

[0591] (III-4) forming a resist upper layer film on the organic thin film using a photoresist material;

[0592] (III-5) exposing the resist upper layer film to pattern exposure and then developing the film with a developer to form a pattern on the resist upper layer film;

[0593] (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 patterned resist upper layer film as a mask;

[0594] (III-7) a step of transferring the pattern to the metal-containing film by dry etching using the inorganic hard mask intermediate film to which the pattern is transferred as a mask; and

[0595] (III-8) A step of processing the substrate to be processed by using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0596]

[14] : A pattern forming method is a method for forming a pattern on a processed substrate, characterized by comprising the following steps:

[0597] (IV-1) forming a resist underlayer film on a substrate to be processed;

[0598] (IV-2) a step of coating the metal-containing film-forming composition as described in any one of [8] to

[10] on the resist underlayer film, and then performing a heat treatment to form a metal-containing film;

[0599] (IV-3) a step of forming a resist upper layer film on the metal-containing film using a photoresist material; or a step of forming a contact film on the metal-containing film by spin coating and forming a resist upper layer film thereon using a photoresist material;

[0600] (IV-4) exposing the resist upper layer film to pattern exposure and then developing the film with a developer to form a pattern on the resist upper layer film;

[0601] (IV-5) a step of transferring the pattern to the metal-containing film, or the adhesive film and the metal-containing film, by dry etching using the patterned resist upper layer film as a mask;

[0602] (IV-6) a step of 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

[0603] (IV-7) A step of processing the substrate to be processed using the patterned resist underlayer film as a mask to form a pattern on the substrate to be processed.

[0604]

[15] : A method for forming a pattern on a processed substrate, characterized by comprising the following steps:

[0605] (V-1) forming a resist underlayer film on a substrate to be processed;

[0606] (V-2) forming a resist intermediate film, or a combination of an inorganic hard mask intermediate film selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film and an organic thin film on the resist underlayer film;

[0607] (V-3) a step of forming a resist upper film using a photoresist material on the resist intermediate film or the combination of the inorganic hard mask intermediate film and the organic thin film;

[0608] (V-4) exposing the resist upper layer film to pattern exposure and then developing the film with a developer to form a pattern on the resist upper layer film;

[0609] (V-5) a step of transferring the pattern to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film by dry etching using the patterned resist upper film as a mask;

[0610] (V-6) a step of transferring the pattern to the resist underlayer film by dry etching using the resist interlayer film or the inorganic hard mask interlayer film to which the pattern has been transferred as a mask;

[0611] (V-7) After coating the metal-containing film-forming composition as described in any one of [8] to

[10] on the resist underlayer film having the pattern formed thereon, a step of covering the metal-containing film by heat treatment to fill the space between the resist underlayer film patterns with the metal-containing film;

[0612] (V-8) etching back the metal-containing film coated on the resist underlayer film having the pattern formed thereon by chemical stripping agent or dry etching to expose the top surface of the resist underlayer film having the pattern formed thereon;

[0613] (V-9) removing the resist intermediate film or the inorganic hard mask intermediate film remaining on the top surface of the resist underlayer film by dry etching;

[0614] (V-10) removing the resist underlayer film having the pattern formed on the surface exposed by dry etching, thereby forming a reverse pattern of the original pattern on the metal-containing film;

[0615] (V-11) A step of processing the substrate to be processed by using the metal-containing film forming the reverse pattern as a mask to form a reverse pattern on the substrate to be processed.

[0616]

[16] : The pattern forming method of

[13] or

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

[0617] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and any configuration substantially the same as the technical concept described in the claims of the present invention and any configuration that exhibits the same functions and effects are included in the technical scope of the present invention.

[0618] Description of Reference Numerals

[0619] 1: Processed substrate

[0620] 2: Processing layer

[0621] 2a: Pattern (pattern formed on the processed layer)

[0622] 3: Metal-containing films

[0623] 3a: Metal-containing film pattern

[0624] 4: Silicon-containing resist interlayer

[0625] 4a: Silicon-containing resist interlayer pattern

[0626] 5: Resist upper film

[0627] 5a: Resist upper film pattern

[0628] 6: Exposure part

[0629] 7: Resist underlayer film composed of coating type organic underlayer film material

[0630] 7a: Resist lower film pattern composed of coating type organic lower film material

[0631] 8:Metallic film

[0632] 8a: Metal-containing film pattern obtained by inverting the resist lower film pattern

[0633] 9: Base substrate with dense lines and spaces

[0634] 10:Metallic film

[0635] 11: Base substrate with dense lines and spaces

[0636] 12: Metal-containing films

[0637] Delta12: The height difference between the patterned part and the non-patterned part of the metal-containing film 12

Claims

1. A metal-containing film-forming compound, characterized in that: The compound is represented by the following general formula (M): In the general formula (M), R1 and R2 are each independently an organic group or a halogen atom, and W is a divalent organic group represented by the following general formula (W-1) or (W-2); In the general formula (W-1), l is an integer of 2 to 3, R3 and R4 are each independently a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, a hydrogen atom, or a halogen atom, or R3 and R4 on the same carbon atom together with the carbon atom to which they are bonded form a carbonyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the alkoxy group may also have an ester group or an amide group; and R3 and R4 on the same carbon atom may also be bonded to To form a ring structure, R3 and R4 on adjacent carbons may also be bonded to form a ring structure; in the general formula (W-2), R5 is each independently a substituted or unsubstituted straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, or a halogen atom, the alkyl group, the alkenyl group, the alkynyl group, and the alkoxy group may also have an ester group or an amide group, n is an integer of 0 to 1, m is an integer of 0 to 6, and * is a bonding site with -OSn.

2. The metal-containing film-forming compound according to claim 1, wherein In the general formula (M), R1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated 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, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms.

3. The metal-containing film-forming compound according to claim 1, wherein The R2 is -OC(=O)R2', wherein R2' is a monovalent organic group.

4. The metal-containing film-forming compound according to claim 3, wherein The R2' is the following general formula (A-1) to (A-4) or the following general formula (2) or the following general formula (3); In the general formulas (A-1) to (A-4), Y A1 , Y A2 may be the same as or different from each other, and are a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms; R A is a hydrogen atom, a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms, R A1 It is an organic group represented by the following general formula (1) in which the protecting group is released by the action of one or both of acid and heat to generate one or more hydroxyl groups or carboxyl groups, and * represents the bonding site with the carbonyl group; In the general formula (1), R A2 is an organic group whose protecting group will be removed by the action of one or both of acid and heat, and * indicates A1 or Y A2 The bond of In the general formula (2), X is a divalent organic group having 1 to 31 carbon atoms, B is the following general formula (B), and * indicates the bonding site with the carbonyl group; B = * -YB-RB (B) In the general formula (B), Y B is a substituted or unsubstituted saturated or unsaturated divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted divalent aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted divalent aralkyl group having 7 to 31 carbon atoms, and may be bonded to an adjacent group via an oxygen atom or an NH group, R B is a hydroxyl group or any one of the structures represented by the following general formulas (B-1) to (B-3); * represents the bonding site with the carbonyl group; In the general formulas (B-1) to (B-3), R B1 is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents B The bond of In the general formula (3), X is a divalent organic group having 1 to 31 carbon atoms, C is a group represented by the following general formulas (C-1) to (C-4), and * represents the bonding site to the carbonyl group; In the general formulas (C-1) and (C-3), R C1 are each independently a hydrogen atom or a methyl group, and they may be the same or different from each other in the same formula; in (C-3) to (C-4), R C2 It is a hydrogen atom, or a substituted or unsubstituted saturated or unsaturated monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms; * indicates the bonding site to the carbonyl group.

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

6. The metal-containing film-forming compound according to claim 4, wherein In the general formulas (A-1) to (A-4), Y A1 , X in the general formula (2), or X in the general formula (3) is the following general formula (4); In the general formula (4), R a , R b and R C is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, R a and R b They may also be bonded to form a cyclic substituent; *1 and *2 represent the bonding sites with the carbonyl group, respectively, and the substitution positions of *1 and *2 may also be interchangeable.

7. The metal-containing film-forming compound 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 metal-containing film-forming compound in terms of polystyrene determined by gel permeation chromatography is 1.00≤Mw / Mn≤1.

50.

8. A metal-containing film-forming composition which functions as a resist underlayer film material used in semiconductor manufacturing, Its characteristics are: The method comprises (a) the metal-containing film-forming compound according to any one of claims 1 to 7 and (b) an organic solvent.

9. The metal-containing film-forming composition according to claim 8, which can be used as a metal-containing film-forming composition for a resist underlayer film used in a multilayer resist method, and further contains one or more of (c) a cross-linking agent, (d) a surfactant, (e) a fluidity promoter, and (f) an acid generator.

10. The metal-containing film-forming composition according to claim 8, wherein The (b) organic solvent is a mixture of one or more organic solvents having a boiling point of less than 180°C and one or more organic solvents having a boiling point of 180°C or higher.

11. A method for forming a pattern on a processed substrate. The method is characterized by having the following steps: (I-1) a step of applying the metal-containing film-forming composition according to claim 8 onto a substrate to be processed, and then performing a heat treatment to form a metal-containing film; (I-2) forming a resist upper layer film on the metal-containing film using a photoresist material; (I-3) exposing the resist upper layer film to pattern exposure and then developing the film 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 patterned resist upper layer film as a mask; and (I-5) A step of processing the substrate to be processed by using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

12. A method for forming a pattern on a substrate to be processed. The method is characterized by having the following steps: (II-1) Coating on the substrate to be processed A step of forming a metal-containing film by heat treatment after preparing the metal-containing film-forming composition according to claim 8; (II-2) a step of forming a resist intermediate film on the metal-containing film; (II-3) forming a resist upper film on the resist intermediate film using a photoresist material; (II-4) exposing the resist upper layer film to pattern exposure and then developing the film with a developer to form a pattern on the resist upper layer film; (II-5) a step of transferring the pattern to the resist intermediate film by dry etching using the patterned resist upper layer film as a mask; (II-6) a step of transferring the pattern to the metal-containing film by dry etching using the resist intermediate film to which the pattern has been transferred as a mask; and (II-7) A step of processing the substrate to be processed by using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

13. A method for forming a pattern on a processed substrate. The method is characterized by having the following steps: (III-1) a step of applying the metal-containing film-forming composition according to claim 8 onto a substrate to be processed, and then performing a heat treatment to form a metal-containing film; (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride 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 upper layer film on the organic thin film using a photoresist material; (III-5) exposing the resist upper layer film to pattern exposure and then developing the film 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 patterned resist upper layer film as a mask; (III-7) a step of transferring the pattern to the metal-containing film by dry etching using the inorganic hard mask intermediate film to which the pattern is transferred as a mask; and (III-8) A step of processing the substrate to be processed by using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

14. A method for forming a pattern on a processed substrate. The method is characterized by having the following steps: (IV-1) forming a resist underlayer film on a substrate to be processed; (IV-2) a step of coating the metal-containing film-forming composition according to claim 8 on the resist underlayer film and then performing a heat treatment to form a metal-containing film; (IV-3) a step of forming a resist upper layer film on the metal-containing film using a photoresist material; or a step of forming a contact film on the metal-containing film by spin coating and forming a resist upper layer film thereon using a photoresist material; (IV-4) exposing the resist upper layer film to pattern exposure and then developing the film with a developer to form a pattern on the resist upper layer film; (IV-5) a step of transferring the pattern to the metal-containing film, or the adhesive film and the metal-containing film, by dry etching using the patterned resist upper layer film as a mask; (IV-6) a step of 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 patterned resist underlayer film as a mask to form a pattern on the substrate to be processed.

15. A method for forming a pattern on a processed substrate. The method is characterized by having the following steps: (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 silicon oxide film, silicon nitride film, and silicon oxide nitride film and an organic thin film on the resist underlayer film; (V-3) a step of forming a resist upper film using a photoresist material on the resist intermediate film or the combination of the inorganic hard mask intermediate film and the organic thin film; (V-4) exposing the resist upper layer film to pattern exposure and then developing the film with a developer to form a pattern on the resist upper layer film; (V-5) a step of transferring the pattern to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film by dry etching using the patterned resist upper film as a mask; (V-6) a step of transferring the pattern to the resist underlayer film by dry etching using the resist interlayer film or the inorganic hard mask interlayer film to which the pattern has been transferred as a mask; (V-7) a step of coating the metal-containing film-forming composition according to claim 8 on the resist underlayer film having the pattern formed thereon, and then covering the metal-containing film by heat treatment to fill the space between the resist underlayer film patterns with the metal-containing film; (V-8) etching back the metal-containing film coated on the resist underlayer film having the pattern using a chemical stripper or dry etching to expose the top surface of the resist underlayer film having the pattern; (V-9) removing the resist intermediate film or the inorganic hard mask intermediate film remaining on the top surface of the resist underlayer film by dry etching; (V-10) removing the resist underlayer film having the pattern formed on the surface 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 by using the metal-containing film forming the reverse pattern as a mask to form a reverse pattern on the substrate to be processed.

16. The pattern forming method according to claim 13, wherein: The inorganic hard mask intermediate film is formed by a CVD method or an ALD method.

17. The pattern forming method according to claim 15, wherein: The inorganic hard mask intermediate film is formed by a CVD method or an ALD method.

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