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 metal compound which has excellent dry etching resistance with respect to known organic underlayer film materials and also has a high degree of landfill / planarization characteristics; a metal-containing film-forming composition using the compound; and a pattern forming method in which the composition is used in a resist underlayer film material. [Solution] A metal-containing compound for forming a film, which is a reaction product of a compound having two or more diol structures in each molecule and an Sn compound, and which is characterized by being a monomolecular compound containing two or more Sn atoms in each molecule.

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 process; and a pattern forming method using the material. 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, double exposure (double patterning) process is practical in the 28nm node and subsequent generations, and even narrow pitch patterns beyond the optical limit can be formed.

[0003] Then, in the manufacture 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, the alkyl ligands will dissociate through light absorption or 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 kind of organotin polymer 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 7, it is reported that materials using Ti compounds show excellent dry etching resistance to CHF3 / CF4 gas and CO2 / N2 gas.

[0010] On the other hand, as for the problems when using metal compounds in resist underlayer films, the embedding property can be cited. For example, although the heat resistance is not mentioned in the compounds expected to be used in photoresists in Patent Document 6, there is a risk of insufficient heat resistance, embedding, and poor film forming properties because baking at high temperatures is not expected. In addition, although the embedding property is not mentioned in Patent Document 7, generally speaking, metal oxide compounds have large thermal shrinkage during baking, which will induce significant deterioration of filling properties after high-temperature baking, so there is a concern that they are not sufficient as resist underlayer film materials that require high levels of flattening properties, embedding properties, and heat resistance. Although Patent Document 8 reports that the metal compound modified with a specific ligand has 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 9 provides a resist underlayer film material having excellent filling properties after baking at 400°C by mixing the metal compound reported in patent document 8 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. 7028940

[0019] [Patent Document 7] Japanese Patent No. 6189758

[0020] [Patent Document 8] Japanese Patent No. 7050137

[0021] [Patent Document 9] Japanese Patent Publication No. 2022-521531 Summary of the invention

[0022] [Problems to be solved by the invention]

[0023] The present invention is made in view of the above situation, and its purpose is to provide a metal compound that has excellent dry etching resistance to known organic lower layer film materials and also has a high degree of filling / planarization characteristics; a metal-containing film forming composition using the compound; and a pattern forming method using the composition in an anti-etching lower layer film material.

[0024] [Methods to solve the problem]

[0025] In order to solve the above problems, the present invention provides a metal-containing film-forming compound which is a reaction product of a compound having two or more diol structures in the molecule and a Sn compound, and is characterized in that it is a monomolecular compound containing two or more Sn atoms in one molecule.

[0026] If it is the metal-containing film-forming compound of the present invention, it has excellent dry etching resistance relative to known organic lower layer film materials and has a high degree of filling / planarization characteristics. It is possible to provide a metal-containing film-forming composition using the metal compound and a pattern forming method using the composition in an anti-etching lower layer film material.

[0027] The metal-containing film-forming compound may be represented by the following general formula (M-1) or (M-2).

[0028] [Chemistry 1]

[0029]

[0030] In the general formulae (M-1) to (M-2), R1 and R2 are each independently a monovalent organic group or a halogen atom; X1 is selected from a substituted or unsubstituted straight-chain alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 70 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted triazine ring, a substituted or unsubstituted isocyanuric acid, and an n1-valent organic group in a substituted or unsubstituted glycoluril group, wherein n1 is an integer of 2 to 6, and the alkyl group and the aliphatic unsaturated hydrocarbon group may also have an ether group, a thioether group, an ester group, or an amide group; R3 represents a substituent other than a hydrogen atom, and each is independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. an oxy group, 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 carboxyl group, or a halogen atom, wherein l is an integer from 0 to 1, and m1 is an integer from 0 to 5; X2 is a single bond, or a linking portion, wherein the linking portion is a carbonyl group, an ether group, an ester group, or an amide group, or is selected from a substituted or unsubstituted straight-chain alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted 2 to 2 carbon atoms containing one or more double bonds or triple bonds, 0, a substituted or unsubstituted aryl group having 6 to 36 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 36 carbon atoms, and an n2-valent organic group in a substituted or unsubstituted triazine ring, and the alkyl group and the aliphatic unsaturated hydrocarbon group may also have a keto group, an ether group, an ester group, an amide group, an imine group, a lactone ring, and a sultone ring, or a 2×n2-valent organic group in a substituted or unsubstituted saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms that forms a cyclic structure with the aromatic ring, and the hydrocarbon group may also have an ether group, and n2 is an integer from 2 to 4.

[0031] 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.

[0032] If the structure is represented by the above general formula (M-1)~(M-2), a sufficient molecular weight can be ensured so that the sublimation of molecules can be suppressed even at high temperatures, thereby providing a metal-containing film-forming composition that has excellent film-forming, filling and planarizing properties even after high-temperature baking.

[0033] In the above general formulas (M-1) to (M2), R1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms.

[0034] In the above general formulas (M-1) to (M-2), if R1 is in this state, free radical homolysis of the tin-carbon bond will occur during baking, and since free radicals are generated, a crosslinking reaction starting from this will occur, which can improve the hardening property. If the metal-containing film-forming compound has such a structure, heat resistance and thermal hardening properties can be taken into account to a high degree, and when it is used in a metal-containing film-forming composition, a resist underlayer film material with more excellent embedding properties can be provided.

[0035] In the metal-containing film-forming compound of the present invention, it is preferable that the above R2 is -OC(=O)R2' (R2' is a monovalent organic group).

[0036] In the above general formulas (M-1) to (M-2), if R2 is -OC(=O)R2', the symmetry of the compound structure collapses, and a metal-containing film-forming composition having excellent solvent solubility can be provided. If it is -OC(=O)R2', R2' can be freely changed, so if a bulky structure is embedded, further improvements in solubility and thermal fluidity can be expected, 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, a metal-containing film-forming composition having excellent film-forming properties, filling and planarization properties can be provided even after high-temperature baking.

[0037] In the present invention, the above R2' is preferably the following general formulas (A-1) to (A-4) or the following general formula (2) or the following general formula (3).

[0038] [Chemistry 2]

[0039]

[0040] 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 arylalkyl 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 arylalkyl group having 7 to 31 carbon atoms, R A1 It is an organic group represented by the following general formula (1) in which the protective group is removed 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;

[0041] [Chemistry 3]

[0042]

[0043] In the general formula (1), R A2 is an organic group whose protective group will be removed by the action of one or both of acid and heat, and * indicates that A1 or Y A2 The bond of

[0044] [Chemistry 4]

[0045]

[0046] 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;

[0047] [Chemistry 5]

[0048] B=*-Y B -R B (B)

[0049] 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 arylalkyl 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;

[0050] [Chemistry 6]

[0051]

[0052] 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

[0053] [Chemistry 7]

[0054]

[0055] In the general formula (3), X is a divalent organic group having 1 to 31 carbon atoms, C is the following general formulas (C-1) to (C-4), and * indicates the bonding site with the carbonyl group;

[0056] [Chemistry 8]

[0057]

[0058] 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 arylalkyl group having 7 to 31 carbon atoms; * indicates the bonding site to the carbonyl group.

[0059] 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 leave 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 degradation of the flatness and the filling property can be suppressed, and a metal-containing film-forming composition with excellent film-forming properties and flattening properties / filling properties can be provided even after high-temperature baking.

[0060] Furthermore, if R2' is a structure represented by the above-mentioned general formula (2), it will contain a hydroxyl group or any cross-linking group in the structures represented by the above-mentioned 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 only these cross-linking groups are present, a cross-linking reaction will be initiated. Therefore, it has excellent thermal curing properties and can suppress volume shrinkage that would induce deterioration of flatness and filling properties. It can provide a metal-containing film-forming composition that has excellent film-forming properties and flattening properties / filling properties even after high-temperature baking.

[0061] If R2' is the structure represented by the above 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 resist underlayer film material with excellent film-forming properties and planarization properties / filling properties can be provided even after high-temperature baking.

[0062] In the general formulas (A-1) to (A-4), Y 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.

[0063] If Y in the above general formulas (A-1) to (A-4) A1 If X in the general formula (2) or X in the general formula (3) is an unsaturated hydrocarbon having 2 to 20 carbon atoms, the thermal curing property of the metal-containing film-forming compound can be further improved.

[0064] 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 the following general formula (4).

[0065] [Chemistry 9]

[0066]

[0067] 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.

[0068] If Y in the above general formulas (A-1) to (A-4) A1 , when X in the general formula (2) or X in the general formula (3) is the general formula (4), it becomes possible to take into account both thermal fluidity and thermal curing properties to a high degree, and when it is used in a metal-containing film-forming composition, it can provide an anti-etching underlayer film material that exhibits more excellent planarization characteristics / filling characteristics.

[0069] In the above general formula (M-2), m1 is 0 or 1, and when m1=1, R3 is preferably a hydroxyl group.

[0070] In the above general formula (M-2), if m1 is 0 or 1, the tin content will increase, so excellent etching resistance can be expected. If R3 is a hydroxyl group when m1 is 1, although homolysis of the tin-carbon bond will occur during baking, the hydroxyl group easily reacts with free radicals, so the hardening property can be improved. Therefore, a metal-containing film-forming composition with excellent film-forming properties, embedding and etching resistance can be provided even after high-temperature baking.

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

[0072] If the metal-containing film-forming compound has a dispersion within this range, it can be confirmed to be a monomolecular compound and will have better thermal fluidity. Therefore, 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 lower layer film that is flat on the entire substrate.

[0073] The present invention can also provide a metal-containing film-forming composition that functions as a resist underlayer film material used in semiconductor manufacturing, the composition comprising (a) the 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 is possible to provide a resist underlayer film material having excellent dry etching resistance compared to known organic underlayer film materials and having high filling / planarization properties.

[0075] 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.

[0076] Furthermore, 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.

[0077] By providing the metal-containing film-forming compound with thermal fluidity by adding a high-boiling-point solvent, the resist underlayer film-forming composition can achieve both high-level filling and planarizing properties.

[0078] Furthermore, the present invention provides a pattern forming method, which is a method for forming a pattern on a processed substrate, characterized by having the following steps:

[0079] (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;

[0080] (I-2) forming a resist upper layer film on the metal-containing film using a photoresist material;

[0081] (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;

[0082] (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

[0083] (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.

[0084] By using the pattern forming method formed by the above-mentioned two-layer resist process, a fine pattern can be formed on the object to be processed (the substrate to be processed).

[0085] Furthermore, the present invention provides a pattern forming method, which is a method for forming a pattern on a processed substrate, characterized by having the following steps:

[0086] (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;

[0087] (II-2) a step of forming a resist intermediate film on the metal-containing film;

[0088] (II-3) forming a resist upper film on the resist intermediate film using a photoresist material;

[0089] (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;

[0090] (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;

[0091] (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

[0092] (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.

[0093] The pattern forming method formed by the above-mentioned three-layer resist process can form a fine pattern on the workpiece with high precision.

[0094] Furthermore, the present invention provides a pattern forming method, which is a method for forming a pattern on a processed substrate, characterized by having the following steps:

[0095] (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;

[0096] (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;

[0097] (III-3) forming an organic thin film on the inorganic hard mask intermediate film;

[0098] (III-4) forming a resist upper layer film on the organic thin film using a photoresist material;

[0099] (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;

[0100] (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;

[0101] (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

[0102] (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.

[0103] The pattern forming method formed by the above-mentioned four-layer resist process can form a fine pattern on the workpiece with high precision.

[0104] At this time, the inorganic hard mask is preferably formed by a CVD method or an ALD method.

[0105] 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.

[0106] 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:

[0107] (IV-1) forming a resist underlayer film on a substrate to be processed;

[0108] (IV-2) a step of applying 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;

[0109] (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;

[0110] (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;

[0111] (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;

[0112] (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

[0113] (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.

[0114] The pattern forming method formed by the multi-layer resist process can form a fine pattern on the workpiece with high precision.

[0115] Furthermore, the present invention provides a pattern forming method, which is a method for forming a pattern on a processed substrate, characterized by having the following steps:

[0116] (V-1) forming a resist underlayer film on a substrate to be processed;

[0117] (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;

[0118] (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;

[0119] (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;

[0120] (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;

[0121] (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;

[0122] (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;

[0123] (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;

[0124] (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;

[0125] (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;

[0126] (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.

[0127] The pattern forming method formed by the above-mentioned reverse process can form a fine pattern on the workpiece with higher precision.

[0128] In this case, it is also preferable to form the inorganic hard mask by CVD or ALD.

[0129] 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.

[0130] [Effects of the Invention]

[0131] As described above, the metal-containing film-forming compound of the present invention is a monomolecular compound containing two or more Sn atoms in one molecule, synthesized by reacting a compound having two or more diol structures (including a catechol structure) with a tin compound. Microscopically, it is possible for two hydroxyl groups of diols such as catechol to bond with Sn, and the organic ligand must break two bonds during sublimation, so it will become a tin-containing compound with better heat resistance than a general compound with a univalent ligand (monodentate ligand), and it can suppress the volume shrinkage that induces the deterioration of the filling property. In addition, microscopically, multiple Sn atoms can be introduced into one molecule, so it is possible to design a molecule that increases the Sn content while increasing the molecular weight. In addition, because two other organic groups are contained relative to one Sn atom, it will become a metal-containing film-forming compound with excellent thermal fluidity, and the performance can be adjusted by changing the structure of its organic group. Therefore, when it is used in a metal-containing film-forming composition, volume shrinkage that causes deterioration of the filling property can be suppressed, and a resist underlayer film material having excellent film-forming properties and planarization properties / filling properties even after high-temperature baking can be provided.

[0132] 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.

[0133] Furthermore, the metal-containing film-forming composition comprising the metal-containing film-forming compound of the present invention contains Sn atoms with large EUV light absorption, and therefore has a sensitization effect due to secondary electrons generated thereby during exposure. Furthermore, since the Sn 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 generally maintaining the LWR performance that the resist upper film originally possesses while being highly sensitive. BRIEF DESCRIPTION OF THE DRAWINGS

[0134] [ Figure 1 ] (A) to (F) are illustrations of an example of the pattern forming method of the present invention (three-layer resist process).

[0135] [ 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 of the three-layer resist process).

[0136] [ Figure 3 ] (Q) to (S) are explanatory diagrams of the landfill characteristic evaluation method.

[0137] [ Figure 4 ] (T) and (U) are explanatory diagrams of the flattening characteristic evaluation method. DETAILED DESCRIPTION

[0138] 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.

[0139] The inventors of the present 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, the large tin atoms of EUV 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 and flatten the height difference of the processed substrate after high-temperature baking. The inventors of the present application believe that if it is a diol / catechol-based compound that can bond with two valent tin molecules in one molecule, the bond is not easy to break during baking and the heat resistance can be improved. It was also found that by having multiple such structures in one molecule, the molecular weight can be increased while the tin content can be increased, which will become a metal-containing film-forming composition that exhibits further improvement in heat resistance and excellent etching resistance, and the present invention was completed.

[0140] That is, the present invention is a metal-containing film-forming compound, which is a reaction product of a compound having two or more diol structures in a molecule and a Sn compound, and is characterized in that it is a monomolecular compound containing two or more Sn atoms in one molecule.

[0141] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0142] <Metal-Containing Film-Forming Compound>

[0143] The metal-containing film-forming compound of the present invention is a reaction product of a compound having two or more diol structures (including a catechol structure) in a molecule and a Sn compound, and is characterized in that it is a monomolecular compound containing two or more Sn atoms in one molecule. This compound can be used as a metal-containing film-forming composition that functions as a resist underlayer film material used in semiconductor manufacturing.

[0144] In the present invention, the compound having a diol structure refers to a compound (polyol) having two or more hydroxyl groups (-OH) in the molecule. For such compounds, examples include aliphatic diols having two hydroxyl groups in the molecule, aromatic diols, triols and tetraols having three or more hydroxyl groups in the molecule. The substitution position of the hydroxyl group in the molecule of aliphatic hydrocarbons (straight chain, branched, cyclic, saturated or unsaturated), aromatic hydrocarbons (these hydrocarbons are substituted or unsubstituted, and may have heteroatoms at any position) is not particularly limited. It is more ideal to have a 1,2-diol having a hydroxyl group on two adjacent carbon atoms, or a 1,3-diol having a hydroxyl group on one carbon atom and a carbon atom at the β position of the carbon atom, and it is more ideal to have a compound having a 1,2-diol structure.

[0145] The 1,2-diol structure also includes a structure having hydroxyl groups on two adjacent carbon atoms of the aromatic ring.

[0146] Examples of compounds having a 1,2-diol structure include alkanediols having 2 to 70 carbon atoms which may have a substituent (having a hydroxyl group on two adjacent carbon atoms), alicyclic diols having 3 to 70 carbon atoms which may have a substituent (having a hydroxyl group on two adjacent carbon atoms constituting a ring), catechol derivatives such as catechol, 3-methylcatechol, 4-methylcatechol, and gallol, and heterocyclic compounds having a hydroxyl group on two adjacent carbon atoms constituting a ring such as N-benzoyl-3,4-dihydroxypyrrolidine.

[0147] The compound having a diol structure may be a compound containing a hydroxyl group and a carboxyl group (COOH) such as α-hydroxycarboxylic acid, or a compound having two or more hydroxyl groups in the final structure. Examples of the latter include β-diketone such as acetylacetone.

[0148] Examples of the compound having a 1,3-diol structure include 1,3-propylene glycol and other alkanediols having 3 to 70 carbon atoms which may have a substituent.

[0149] The compound having a diol structure of the present invention is a compound (complex) in which a diol is coordinated to Sn as a central metal, and examples thereof include compounds in which 1,2-diol (ligand) forms a 5-membered ring with Sn. If an aromatic 1,2-diol such as catechol or 2,3-naphthalene diol is coordinated to Sn to form a 5-membered ring, a hard structure will be obtained.

[0150] In the case of such a compound, it is possible to bond Sn to two hydroxyl groups of catechol and diol at a microscopic level, and when the bond with the organic ligand is broken, two Sn-O bonds must be broken at the same time, so it becomes a tin-containing compound with better heat resistance than a general compound with a monovalent ligand, and the volume shrinkage that induces the deterioration of the embedding property can be suppressed, so that even after high-temperature baking, the film forming property, embedding and planarization characteristics are still excellent. In addition, at a microscopic level, multiple Sn atoms can be introduced into one molecule, so it is also possible to increase the tin content while increasing the molecular weight, and a resist underlayer film material with excellent heat resistance and etching resistance can be provided.

[0151] The metal-containing film-forming compound is preferably a metal-containing film-forming compound represented by the following general formulas (M-1) to (M-2).

[0152] [Chemistry 10]

[0153]

[0154] In the general formulae (M-1) to (M-2), R1 and R2 are each independently a monovalent organic group or a halogen atom; X1 is selected from a substituted or unsubstituted straight-chain alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 70 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted triazine ring, a substituted or unsubstituted isocyanuric acid, and an n1-valent organic group in a substituted or unsubstituted glycoluril group, wherein n1 is an integer of 2 to 6, and the alkyl group and the aliphatic unsaturated hydrocarbon group may also have an ether group, a thioether group, an ester group, or an amide group; R3 represents a substituent other than a hydrogen atom, and each is independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. an oxy group, 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 carboxyl group, or a halogen atom, wherein l is an integer from 0 to 1, and m1 is an integer from 0 to 5; X2 is a single bond, or a linking portion, wherein the linking portion is a carbonyl group, an ether group, an ester group, or an amide group, or is selected from a substituted or unsubstituted straight-chain alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted 2 to 2 carbon atoms containing one or more double bonds or triple bonds, 0, a substituted or unsubstituted aryl group having 6 to 36 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 36 carbon atoms, and an n2-valent organic group in a substituted or unsubstituted triazine ring, and the alkyl group and the aliphatic unsaturated hydrocarbon group may also have a keto group, an ether group, an ester group, an amide group, an imine group, a lactone ring, and a sultone ring, or a 2×n2-valent organic group in a substituted or unsubstituted saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms that forms a cyclic structure with the aromatic ring, and the hydrocarbon group may also have an ether group, and n2 is an integer from 2 to 4.

[0155] 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-1) to (M-2), a sufficient molecular weight can be ensured, so the rapid volume shrinkage during baking can be suppressed, and the film-forming property, filling property, and flattening property are excellent. The tin content can also be increased, so it can become a metal-containing film-forming compound with excellent etching resistance.

[0156] If it is a metal-containing film-forming compound represented by the above-mentioned general formula (M-1) to (M-2), since a sufficient molecular weight can be ensured, the rapid volume shrinkage during baking can be suppressed, and the film-forming property, filling property, and flattening property are excellent, and the tin content can also be increased, so it will become a metal-containing film-forming compound that can provide a metal-containing film with excellent etching resistance.

[0157] In the above general formulas (M-1) to (M-2), R1 and R2 are each independently a monovalent organic group or a halogen atom. Considering the viewpoint of raw material acquisition and synthesis, it is preferably an alkyl group, an ester group, an alkoxy group, or a chloro group. Considering the viewpoint of solvent solubility, it is more preferable that the structures are different in the same compound. In addition, considering thermal fluidity, it is more preferable that R1 and R2 are a combination of an alkyl group and an ester group.

[0158] In the above general formula (M-1), X1 is an n1-valent organic group selected from a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 70 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted triazine ring, a substituted or unsubstituted isocyanuric acid group, and a substituted or unsubstituted glycoluril group, wherein n1 is an integer of 2 to 6, and the alkyl group and the aliphatic unsaturated hydrocarbon group may also have an ether group, a thioether group, an ester group, or an amide group. Specific examples of the above general formula (M-1) include the following, but are not limited thereto.

[0159] [Chemistry 11]

[0160]

[0161] In the above formula, n is each independently an integer greater than or equal to 0, and applies only to the above formula.

[0162] [Chemistry 12]

[0163]

[0164] In the above general formula (M-2), specific examples of R3 include the following, but are not limited to these. In the following formula, * represents an atomic bond to an aromatic ring.

[0165] [Chemistry 13]

[0166]

[0167] In the above general formula (M-2), l is an integer of 0 to 1, and l is preferably 0 from the viewpoint of increasing the Sn content.

[0168] In the above general formula (M-2), X2 is a single bond, or a linking portion, and the linking portion is a carbonyl group, an ether group, an ester group, or an amide group, or is selected from a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 36 carbon atoms, a substituted or unsubstituted A substituted arylalkyl group having 6 to 36 carbon atoms, and an n2-valent organic group in a substituted or unsubstituted triazine ring, and the alkyl group, and an aliphatic unsaturated hydrocarbon group may also have a ketone group, an ether group, an ester group, an amide group, an imine group, a lactone ring, and a sultone ring, or a 2×n2-valent organic group in a substituted or unsubstituted saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms that forms a ring structure with an aromatic ring, and the hydrocarbon group may also have an ether group, and n2 is an integer of 2 to 4. Specific examples of the above general formula (M-2) include the following, but are not limited to these.

[0169] [Chemistry 14]

[0170]

[0171] In the above general formulas (M-1) to (M-2), R1 is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms. From the perspective of suppressing sublimates, an unsubstituted alkyl group having 1 to 20 carbon atoms is more ideal. Considering the ease of obtaining raw materials, an n-butyl group is particularly ideal.

[0172] If this is a metal-containing film-forming compound, since the compound contains a tin-alkyl bond, the bond will break during baking to generate a free radical, so a cross-linking reaction will occur with the free radical as the starting point, and the thermal curing property is excellent. Therefore, even after high-temperature baking, a resist underlayer film material with excellent film-forming properties, filling properties and planarization properties can be provided.

[0173] In the above general formulae (M-1) to (M-2), from the viewpoint of solvent solubility, R2 is preferably -OC(=O)R2' (R2' is a monovalent organic group).

[0174] If this 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, it can be expected that the solubility and thermal fluidity obtained by embedding a bulky structure can be further improved, and it can also be made to have a 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 embedding property can be suppressed. In this way, a resist underlayer film material with excellent film forming properties, embedding and planarization characteristics can be provided even after high-temperature baking.

[0175] 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).

[0176] [Chemistry 15]

[0177]

[0178] 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 arylalkyl 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 arylalkyl group having 7 to 31 carbon atoms, R A1 It is an organic group represented by the following general formula (1) in which the protective group is removed 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.

[0179] [Chemistry 16]

[0180]

[0181] In the general formula (1), R A2 is an organic group whose protective group will be removed by the action of one or both of acid and heat, and * indicates that A1 or Y A2 The bond of .

[0182] 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 arylalkyl 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 arylalkyl group having 7 to 31 carbon atoms, R A1 It is an organic group represented by the general formula (1) above, in which the protective group is removed by the action of one or both of acid and heat to generate one or more hydroxyl groups or carboxyl groups. In consideration of thermal fluidity, (A-4) is more preferable, and in consideration of increasing the tin content, (A-1) is more preferable.

[0183] 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.

[0184] [Chemistry 17]

[0185]

[0186] In the above general formula (A-3), R A It is a hydrogen atom, a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms. In view of the suppression of sublimates and the increase in the Sn content, hydrogen is preferably used.

[0187] In the above general formula (1), R A2 It is an organic group from which a thermally acid-labile group leaves due to the action of one or both of acid and heat, preferably a tertiary hydrocarbon group or a group forming an acetal structure together with an adjacent oxygen atom, and particularly preferably a tertiary hydrocarbon group.

[0188] 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.

[0189] [Chemistry 18]

[0190]

[0191] [Chemistry 19]

[0192]

[0193] [Chemistry 20]

[0194]

[0195] [Chemistry 21]

[0196]

[0197] As for the group forming the above-mentioned acetal structure, if it is an organic group that can cause the unstable group to leave or break 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.

[0198] [Chemistry 22]

[0199]

[0200] [Chemistry 23]

[0201]

[0202] [Chemistry 24]

[0203]

[0204] 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 The tin content of the tin-containing film is increased because the tin-containing film is formed because the tin-containing film is formed in a composition for forming a metal-containing film. The ...

[0205] When a metal-containing film is formed using an organic tin compound, the organic group bonded to the Sn atom at intervals of the C atom will leave and generate free radicals at the same time. The generated free radicals 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 leave at the same time as the above reaction, a large film shrinkage will occur during baking. However, the above-mentioned compound has a thermally acid-labile group at the end, and the thermally acid-labile group will leave and generate a hydroxyl or carboxyl group during baking. The OH and α-hydrogen at the end they have will easily 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-forming composition with excellent landfill properties can be provided.

[0206] [Chemistry 25]

[0207]

[0208] [Chemistry 26]

[0209]

[0210] 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.

[0211] [Chemistry 27]

[0212] B=*-Y B -R B (B)

[0213] 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 (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 arylalkyl 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.

[0214] [Chemistry 28]

[0215]

[0216] 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 atoms, q represents 0 or 1, and * representsB The bond of .

[0217] In the above general formula (2), X is a divalent organic group having 1 to 31 carbon atoms, B is the above general formula (B), and * indicates the bonding site with the carbonyl group. 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 arylalkyl 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 It is preferably a hydroxyl group or any one of the structures represented by the above general formulae (B-1) to (B-3). In the above general formulae (B-1) to (B-3), R B1 It is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and is preferably a hydrogen atom from the viewpoint of suppressing sublimation.

[0218] Preferred structures of the general formula (B) include the following structures, but are not limited thereto. In the following formula, * represents an atomic bond with a carbonyl group.

[0219] [Chemistry 29]

[0220]

[0221] If such a metal-containing film-forming compound is used, it will be a metal-containing film-forming compound with excellent solvent solubility and thermal fluidity. B Since it contains hydroxyl groups or unsaturated bonds, when it is used in a metal-containing film-forming composition, it undergoes a cross-linking reaction during baking, resulting in excellent thermal curing properties. It also reacts with free radicals generated by the breaking of the tin-carbon bond, thereby promoting the cross-linking reaction and having excellent thermal curing properties. Therefore, volume shrinkage can be suppressed, and a metal-containing film-forming composition having excellent film-forming properties and planarization / filling properties can be provided even after high-temperature baking.

[0222] [Chemistry 30]

[0223]

[0224] 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.

[0225] [Chemistry 31]

[0226]

[0227] In the general formulas (C-1) and (C-3), R C1are 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 arylalkyl group having 7 to 31 carbon atoms. * indicates the bonding site to the carbonyl group.

[0228] 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 arylalkyl 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 suppression of sublimates, a hydrogen atom is preferable, and from the viewpoint of thermal fluidity, the above-described structures other than a hydrogen atom are preferable.

[0229] 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.

[0230] [Chemistry 32]

[0231]

[0232] If it is a metal-containing film-forming compound having such a structure, since 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, since 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 it can provide a metal-containing film-forming composition with excellent filling / planarization characteristics.

[0233] 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) are preferably exemplified by the following structures, but are not limited thereto. In addition, in the following formula, * represents the bonding site with the carbon atom of the carbonyl group or * in formulas (A-1) to (A-4), formula (2), and formula (3).

[0234] [Chemistry 33]

[0235]

[0236] In the above general formulas (A-1) to (A-4), Y A1 Preferably, X in the above general formula (2) or X in the above general formula (3) is a substituted or unsubstituted divalent unsaturated hydrocarbon having 2 to 20 carbon atoms.

[0237] In the above general formulas (A-1) to (A-4), Y A1 When X in the general formula (2) or X in the general formula (3) is such a divalent unsaturated hydrocarbon, the thermal curability of the metal-containing film-forming compound can be further improved.

[0238] 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 the following general formula (4).

[0239] [Chemistry 34]

[0240]

[0241] 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.

[0242] For example, the carboxylic acid raw material containing the above 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. The presence of such isomers can suppress crystallinity, 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.

[0243] [Chemistry 35]

[0244]

[0245] 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.

[0246] In the general formula (M-2), m1 is preferably 0 or 1 from the viewpoint of increasing the tin content, and when m1 is 1, R3 is preferably a hydroxyl group from the viewpoint of curability.

[0247] In the above general formula (M-2), if m1 is 0 or 1, the tin content rate is increased, so excellent etching resistance can be expected. If R3 is a hydroxyl group when m1 is 1, free radical homolysis of the tin-carbon bond occurs during baking, but since the hydroxyl group easily reacts with free radicals, the hardening property can be improved. Therefore, a metal-containing film-forming composition having excellent film-forming properties, embedding and etching resistance even after high-temperature baking can be provided.

[0248] The metal-containing film-forming compound preferably has a characteristic that a ratio Mw / Mn of a weight average molecular weight Mw and a number average molecular weight Mn in terms of polystyrene measured by gel permeation chromatography is 1.00≤Mw / Mn≤1.50.

[0249] 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 having repeating units to approach Mw / Mn=1.00 without using a special polymerization method, and Mw / Mn will become a value exceeding 1 due to the distribution of Mw. In order to distinguish monomolecular compounds from polymers, the present invention defines 1.00≤Mw / Mn≤1.50 as an indicator of monomolecularity.

[0250] If the metal-containing film-forming compound has a dispersion degree within this range, it can be confirmed to be a monomolecular compound and the thermal fluidity will be better. Therefore, 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 lower layer film that is flat on the entire substrate.

[0251] <Metal-Containing Film-Forming Composition>

[0252] Furthermore, the present invention can provide a metal-containing film-forming composition, which is a metal-containing film-forming composition that functions as a resist underlayer film material used in semiconductor manufacturing, and is characterized in that it contains (a) the above-mentioned metal-containing film-forming compound of the present invention and (b) an organic solvent.

[0253] Such a metal-containing film-forming composition contains an organic tin compound having excellent heat resistance and thermal fluidity, and thus can provide a resist underlayer film material having excellent dry etching resistance compared to known organic underlayer film materials and having high filling / planarization properties.

[0254] 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.

[0255] <(b) Organic Solvents>

[0256] 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.

[0257] 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.

[0258] (High boiling point solvent)

[0259] In the 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 180°C or higher (high boiling point solvent).

[0260] 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 or disperse 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.

[0261] The high boiling point solvent can be appropriately selected from the above-mentioned ones according to the temperature at which the resist underlayer 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 underlayer film with excellent filling / planarization characteristics can be formed. In addition, 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.

[0262] The amount of the organic solvent to be added is preferably in the range of 200 to 10,000 parts by mass, more preferably 250 to 5,000 parts by mass, based on 100 parts by mass of the (a) metal-containing film-forming compound.

[0263] 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.

[0264] <Resist Underlayer Film Forming Composition>

[0265] 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.

[0266] Hereinafter, components contained in the 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.

[0267] [(c) Cross-linking agent]

[0268] In the resist lower film forming composition of the present invention, in order to improve the compactness of the film and suppress the intermixing with the resist upper film, (c) a crosslinking agent may also be further contained. 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.

[0269] 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.

[0270] Specific examples of the acrylate crosslinking agent include dipentatriol hexaacrylate.

[0271] 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.

[0272] 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.

[0273] Specific examples of the urea crosslinking agent include dimethoxymethylated dimethoxyethylene urea, alkoxy and / or hydroxyl-substituted products thereof, and partial self-condensates thereof.

[0274] Specific examples of the β-hydroxyalkylamide crosslinking agent include N,N,N′,N′-tetrakis(2-hydroxyethyl)adipamide.

[0275] Specific examples of the isocyanurate-based crosslinking agent include triglycidyl isocyanurate and triallyl isocyanurate.

[0276] Specific examples of the aziridine crosslinking agent include 4,4′-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate].

[0277] 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.

[0278] Specific examples of the polynuclear phenol crosslinking agent include compounds represented by the following general formula (XL-1).

[0279] [Chemistry 36]

[0280]

[0281] 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.

[0282] 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.

[0283] 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.

[0284] [Chemistry 37]

[0285]

[0286] [Chemistry 38]

[0287]

[0288] Examples of the epoxy crosslinking agent and the oxetane crosslinking agent include monomolecular type and polymer type. Specific examples of the monomolecular type include those shown below, but are not limited to these.

[0289] [Chemistry 39]

[0290]

[0291] The above compounds are commercially available, but epoxy-based crosslinking agents and oxetane-based crosslinking agents can also be obtained by reacting hydroxyl groups 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 with 1 to 20 carbon atoms or an unsaturated monovalent organic group with 2 to 20 carbon atoms, a substituted or unsubstituted aryl group with 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group with 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.

[0292] [Chemistry 40]

[0293]

[0294] 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.

[0295] [Chemistry 41]

[0296]

[0297] 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; and vinyl silanes. Moreover, the weight average molecular weight of these polymers is 1,000 to 20,000, and the GPC dispersion is preferably 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.

[0298] [Chemistry 42]

[0299]

[0300] 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-.

[0301] In the general formula (XL-2), R8 preferably has the following characteristics from the viewpoint of curability: the number of epoxy groups + oxetane groups > the number of hydroxyl groups; more preferably, the number of epoxy groups + oxetane groups > the number of hydroxyl groups*2.

[0302] [Chemistry 43]

[0303]

[0304] 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).

[0305] [Chemistry 44]

[0306]

[0307] In the above formula, the dotted lines represent atomic bonds.

[0308] <(d) Surfactant>

[0309] 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).

[0310] <(e) Flowability Enhancer>

[0311] 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.

[0312] 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.

[0313] 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).

[0314] [Chemistry 45]

[0315]

[0316] 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.

[0317] [Chemistry 46]

[0318]

[0319] 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.

[0320] <(f) Acid Generator>

[0321] The resist underlayer film forming composition of the present invention may further promote the leaving 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.

[0322] 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).

[0323] <Resist Underlayer Film Formation Method>

[0324] 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.

[0325] 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. If the damage to the device and the influence on the deformation of the wafer are taken into consideration, it is more preferable 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.

[0326] 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.

[0327] By calcining the metal-containing film of the present invention with a composition 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 less than 1000ppm, and more preferably less than 100ppm (volume basis). If the oxidation of the metal-containing film in baking is prevented, absorption will increase, and etching resistance will not be reduced, so it is more ideal.

[0328] <Pattern Formation Method Using Resist Underlayer Film Forming Composition>

[0329] Furthermore, the present invention provides a pattern forming method, characterized in that, as a pattern forming method formed 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.

[0330] The resist upper layer film of 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.

[0331] Furthermore, the present invention provides a pattern forming method, characterized in that it is a pattern forming method formed by a three-layer resist process using such a metal-containing film-forming composition, and 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.

[0332] 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.

[0333] 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)).

[0334] 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.

[0335] As 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. In particular, 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 high and the substrate reflection will become high, 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%. As 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.

[0336] In addition, the present invention provides a pattern forming method, characterized in that, as a pattern forming method formed 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 metal-containing film, forming an organic anti-reflective film (BARC) or a close contact film on the silicon-containing resist intermediate film, and using a photoresist material to form a BARC or close contact 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.

[0337] 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.

[0338] 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.

[0339] 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.

[0340] In addition, in the present invention, as a pattern forming method formed 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 to 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 the patterned resist lower layer film is used again 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.

[0341] 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.

[0342] 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.

[0343] 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.

[0344] 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.

[0345] The patterning method of the resist upper layer film is preferably patterning by optical lithography with a wavelength of 5 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0346] In addition, it is preferable that the development method in the above-mentioned pattern forming method is set to development with an alkali or an organic solvent.

[0347] 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, a silicon-containing resist intermediate film pattern and an inorganic hard mask pattern are formed.

[0348] 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.

[0349] 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-dielectric constant insulating 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.

[0350] 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.

[0351] In addition, the object to be processed (substrate to be processed) is not particularly limited, and a substrate such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc. is used, and a layer to be processed is formed 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 the thickness can be generally formed to 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 can be made of different materials.

[0352] 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.

[0353] <Tone-reversal pattern forming method using a metal-containing film-forming composition>

[0354] 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.

[0355] 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.

[0356] 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)).

[0357] 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)).

[0358] 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.

[0359] 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.

[0360] In the above-mentioned tonal 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) with a height 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, it has excellent resistance to dry etching using Freon-based gases, 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.

[0361] [Example]

[0362] 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 measured by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent were obtained to obtain dispersity (Mw / Mn).

[0363] [Synthesis example]

[0364] In the following synthesis examples and comparative examples, the following tin compounds Sn: (Sn-1) to (Sn-5), raw material group X: (X-1) to (X-12), and raw material group G: (G-1) to (G-7) were used. Each raw material group is shown below.

[0365] Tin compounds Sn:

[0366] [Chemistry 47]

[0367]

[0368] Raw material group X:

[0369] [Chemistry 48]

[0370]

[0371] Raw material group G:

[0372] [Chemistry 49]

[0373]

[0374] [Synthesis Example 1] Synthesis of Metal-Containing Film-Forming Compound (A-1)

[0375] 5.0 g of the tin compound (Sn-4), 1.9 g of the raw material (X-1) 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-1).

[0376] (A-1): Mw=554, Mw / Mn=1.04

[0377] [Synthesis Example 2] Synthesis of Metal-Containing Film-Forming Compound (A-2)

[0378] 5.0 g of the tin compound (Sn-1), 1.6 g of the raw material (X-2) 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-2).

[0379] (A-2): Mw=890, Mw / Mn=1.09

[0380] [Synthesis Example 4] Synthesis of Metal-Containing Film-Forming Compound (A-4)

[0381] 5.0 g of the tin compound (Sn-5), 4.7 g of the raw material (X-4) 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).

[0382] (A-4): Mw=1530, Mw / Mn=1.26

[0383] [Synthesis Examples 3, 5 to 8] Synthesis of Metal-Containing Film-Forming Compounds (A-3), (A-5) to (A-8)

[0384] Except that the tin compound Sn and the above raw material group X were used in the feed amounts shown in Tables 1-1 and 1-2, (A-3), (A-5) to (A-8) were obtained under the same reaction conditions as in Synthesis Example 1. The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) of these compounds were determined. The results are shown in Table 2.

[0385] [Synthesis Examples 9 to 14] Synthesis of Metal-Containing Film-Forming Compounds (A-9) to (A-14)

[0386] Except that the above-mentioned raw material group X and raw material group G were used in the feed amounts shown in Table 1-2, (A-9) to (A-14) were obtained under the same reaction conditions as in Synthesis Example 4. The weight average molecular weight (Mw) and dispersity (Mw / Mn) of these compounds were determined. The results are shown in Table 2.

[0387] [Table 1-1]

[0388]

[0389]

[0390] [Table 1-2]

[0391]

[0392]

[0393] [Synthesis of Metal-Containing Film-Forming Compound (R-1) for Comparative Example]

[0394] 5.0 g of the tin compound (Sn-2), 11.4 g of the raw material group G (G-7), 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-1).

[0395] [Chemistry 50]

[0396]

[0397] [Synthesis of Metal-Containing Film-Forming Compound (R-2) for Comparative Example]

[0398] 5.0 g of the tin compound (Sn-2), 6.8 g of the raw material group X (X-12), and 50 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).

[0399] [Chemistry 51]

[0400]

[0401] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) of these compounds were determined. The results are shown in Table 2.

[0402] [Table 2]

[0403] Compound M Mw / Mn A-1 554 1.04 A-2 890 1.09 A-3 921 1.12 A-4 1530 1.26 A-5 602 1.11 A-6 495 1.03 A-7 563 1.09 A-8 598 1.08 A-9 864 1.18 A-10 610 1.22 A-11 638 1.34 A-12 589 1.41 A-13 608 1.37 A-14 614 1.45 R-1 260 1.02 R-2 356 1.07

[0404] [Synthesis of Metal-Containing Film-Forming Compound (R-3) for Comparative Example]

[0405] As the metal-containing compound intended to be used as a photoresist, a tin compound reported in [Synthesis Example 8] of Japanese Patent No. 7028940 was synthesized.

[0406] 3 g of isopropyltriphenyltin and 1.4 g of succinic acid were dissolved in 20 ml of acetonitrile and refluxed for 24 hours. After the reaction, the solvent was removed under reduced pressure to obtain a tin-containing compound (R-3).

[0407] [Chemistry 52]

[0408]

[0409] [Synthesis of Metal-Containing Film-Forming Compound (R-4) for Comparative Example]

[0410] Add 10g of catechol, 6.6g of formaldehyde, and 30g of PGME (propylene glycol monomethyl ether), and homogenize at an internal temperature of 100°C. Then, pre-mix, slowly drop a homogenized mixture of 0.2g of p-toluenesulfonic acid monohydrate and 3.0g of PGME, and react at an internal temperature of 120°C for 8 hours. After the reaction is terminated, add 300ml of MIBK, wash 4 times with 200ml of pure water, and dry the organic layer under reduced pressure. Then, add 22g of tin raw material (Sn-2) and 300g of toluene, and stir at 130°C for 8 hours. Remove the solvent after the reaction by decompression to obtain (R-4).

[0411] [Chemistry 53]

[0412]

[0413] [Synthesis of Metal-Containing Film-Forming Compound (R-5) for Comparative Example]

[0414] 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.

[0415] 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-5) (compound concentration 20 mass %). Its polystyrene-equivalent molecular weight was measured, Mw=1,100.

[0416] [Synthesis of Organic Film-Forming Resin (R-6) for Comparative Example]

[0417] 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 and washed twice with 500 g of hexane for recovery. The recovered crystals were vacuum dried at 70°C to obtain resin (R-6).

[0418] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC. The results are as follows.

[0419] (R-6): Mw=3,300, Mw / Mn=2.54

[0420] [Chemistry 54]

[0421]

[0422] [Metal-containing film-forming composition UDL-1]

[0423] The metal-containing film-forming compound (A-1) was dissolved in a solvent containing 0.5% by mass of propylene glycol monomethyl ether acetate (PGMEA) or cyclohexanone (CyHO) as a surfactant FC-4430 (manufactured by Sumitomo 3M Co., Ltd.) at the ratio shown in Table 3, and filtered with a 0.2 μm membrane filter to prepare a metal-containing film-forming composition (UDL-1).

[0424] [Preparation of Metal-Containing Film-Forming Compositions (UDL-2 to 18) and Metal-Containing Film-Forming Compositions for Comparative Examples (Comparative Examples UDL-1 to 6)]

[0425] 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 3. In Table 3, "-" means 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 following formula (TAG-1) was used as the thermal acid generator (TAG).

[0426] [Crosslinking agent]

[0427] The cross-linking agent (C-1) used in the metal-containing film-forming composition is shown below.

[0428] [Chemistry 55]

[0429]

[0430] [Synthesis Example of Fluidity Improver Polymer] Synthesis of Fluidity Improver Polymer (F-1)

[0431] 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).

[0432] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC. The results are as follows.

[0433] (F-1): Mw=8,500, Mw / Mn=3.46

[0434] [Chemistry 56]

[0435]

[0436] [Thermal acid generator]

[0437] The thermal acid generator (TAG-1) used in the metal-containing film-forming composition is shown below.

[0438] [Chemistry 57]

[0439]

[0440] [Table 3]

[0441]

[0442]

[0443] As shown in Table 3, the metal-containing film-forming compositions UDL-1 to 7 of the present invention can be prepared as solutions with cyclohexanone, and sufficient solubility was confirmed. In addition, UDL-8 and UDL-9 to 14, which were also used in the reaction with raw material group G and whose molecular symmetry was greatly collapsed, can be prepared with PGMEA, and excellent solvent solubility was confirmed. In addition, the comparative example compound (R-4) of a polymer compound that can introduce multiple tins is not a monomolecular compound, and it does not completely dissolve in PGMEA and CyHO, and a solution cannot be prepared.

[0444] [Evaluation of heat resistance and solvent resistance]

[0445] The metal-containing film-forming composition (UDL-1 to 18, comparative examples UDL-1 to 3, 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 4 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).

[0446] 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 4 below.

[0447] [Table 4]

[0448]

[0449]

[0450] As shown in Table 4, the residual film rate ((b / a)×100) of the metal-containing film-forming composition of the present invention (Examples 1-1 to 1-18) after high-temperature additional baking at 250°C was 65% or more, and it can be understood that the film under the resist has the required high-temperature baking resistance. On the other hand, the residual film rates ((b / a)×100) of Comparative UDL-1 and Comparative UDL-2 using similar tin compounds after high-temperature additional baking at 250°C were 43% and 61%, respectively, indicating that the heat resistance of the compound of the present invention is relatively excellent. In addition, when comparing Examples 1-19 to 1-21 and Comparative Examples 1-4 to 1-5, which were subjected to high-temperature additional baking at 350°C, the residual film rate ((b / a)×100) of Examples 1-19 to 1-21 was 48% or more, while that of Comparative Examples 1-4 to 1-5 was 8% and 35%, respectively, confirming that the compound of the present invention still exhibits excellent heat resistance even when baked at 350°C. It is believed that this is because the compound of the present invention is bonded to tin at two organic ligands like a chelate, so the tin and the organic group of the parent core are not easily cut off, and because the molecular weight becomes large by introducing multiple tin atoms into one molecule, sublimation is inhibited. In addition, the film subjected to high-temperature additional baking treatment has a residual film rate ((c / b)×100) of 98% or more after PGMEA rinsing treatment, which can be understood that a cross-linking reaction occurs and exhibits sufficient solvent resistance. In UDL10~14, which uses raw material group G with more unsaturated bonds and carboxylic acids generated by thermal acid removal, the residual film rate ((c / b)×100) after PGMEA rinsing treatment is 99.5% or more, which can be understood that the cross-linking reaction is further promoted and more sufficient solvent resistance is exhibited.

[0451] The residual film rate after baking of UDL-15 to which a crosslinking agent (C-1) was added increased from 91% to 93% compared to UDL-8 to which no crosslinking agent was added. This is believed to be the result of efficient crosslinking due to the crosslinking agent and suppression of sublimates. In addition, when comparing UDL-13 and UDL-17 to which a thermal acid generator (TAG-1) was added, the residual film rate after PGMEA rinsing treatment ((c / b)×100) of UDL-13 after baking at 250°C was 99.6%, while the residual film rate after baking at 200°C and PGMEA rinsing treatment ((c / b)×100) of UDL-17 was 100%, which is the result of increased curability. This is believed to be the result of the efficient occurrence of the crosslinking reaction caused by the leaving group due to the addition of the thermal acid generator.

[0452] In addition, Comparative Examples 1-3 using the tin compound reported in [Synthesis Example 8] of Japanese Patent No. 7028940 as a tin compound different from the present invention, and Comparative Examples 1-6 using the titanium compound reported in [Synthesis Example A-II] of Japanese Patent No. 6189758 as a metal-containing compound different from the present invention for film-forming, showed sufficient solvent resistance, but the difference in film thickness before and after high-temperature additional baking treatment was large, which is understood to be due to the large volume shrinkage caused by high-temperature baking compared to the metal-containing film-forming compound of the present invention. It is believed that in Comparative Examples 1-3, although there are two tin atoms in one molecule like the present invention, the two tin atoms are bonded by a straight-chain divalent organic group, so the Sn-O bond connecting the two tin atoms itself becomes easy to break, and although there is a ring structure like the present invention, it is a 7-membered ring, and the heat resistance is insufficient because of these two reasons, the thermal stability is poor and the sublimation products are large.

[0453] [Landfill characteristics evaluation]

[0454] The metal-containing film-forming compositions (UDL-1 to 18) having good film-forming properties after the solvent resistance evaluation and additional baking and the comparative examples UDL-1 to 3 and 5 having good or film-forming properties were coated on SiO2 wafer substrates having dense line and space patterns (line width 40 nm, line depth 120 nm, and the distance between the centers of two adjacent lines 80 nm), and heated for 60 seconds at the temperature shown in Table 5 using a hot plate to form a metal-containing film with a thickness of 100 nm. 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 can be buried. The results are shown in Table 5. When a metal-containing film-forming composition with poor filling characteristics is used, the uneven substrate cannot be buried well in this evaluation. When a metal-containing film-forming composition with good filling characteristics is 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 resist underlayer film 10. ○ means that it can be filled without large voids, △ means that voids are visually observed, and × means that it cannot be filled.

[0455] [Table 5]

[0456]

[0457]

[0458] As shown in Table 5, Examples 2-1 to 2-15 using the resist metal-containing film-forming composition of the present invention and Comparative Examples 2-1 to 2-3 using similar tin compounds were baked at 250° C., and it was confirmed that dense line and space patterns could be filled without voids, and had good filling characteristics. In addition, when comparing Examples 2-16 to 2-18 baked at 350° C. with Comparative Examples 2-4 and 2-5, while Examples 2-16 to 2-18 using the compounds of the present invention could fill dense line and space patterns without voids, Comparative Examples 2-4 and 2-5 could not be filled or voids occurred. In Comparative Example 2-3 using the tin compound reported in [Synthesis Example 8] of Japanese Patent No. 7028940, which is different from the purpose of the present invention, and Comparative Example 2-6 using the titanium compound reported in [Synthesis Example A-II] of Japanese Patent No. 6189758, voids were also observed at the bottom of the pattern. It is presumed that this is because, as observed in the above-mentioned solvent resistance evaluation, the volume shrinkage due to high-temperature baking of the compound of the present invention is small, so voids do not occur and can be filled, while on the other hand, the comparative example compound with large volume shrinkage is large, so voids occur or cannot be filled.

[0459] [Planarization characteristics evaluation]

[0460] 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 6. In this evaluation, the smaller the height difference is, the better the planarization characteristics are.

[0461] [Table 6]

[0462]

[0463]

[0464] As shown in Table 6, Examples 3-1 to 3-18 using the metal-containing film-forming composition of the present invention (UDL-1 to 18) were confirmed to exhibit excellent flatness compared to Comparative Example 3-3 of the titanium compound reported in [Synthesis Example A-II] of Japanese Patent No. 6189758 Gazette and Comparative Example 3-4 as an organic resist underlayer film. It is believed that this is because the compound of the present invention has a long-chain alkyl group and an asymmetric structure and has excellent thermal fluidity. In addition, it was confirmed that even when baked at 350°C as in Examples 3-16 to 3-18, the same flatness was exhibited.

[0465] In addition, Examples 3-13 and 3-15 to which a high boiling point solvent (D-1) and a fluidity enhancer (F-1) were added showed excellent planarization characteristics compared to Examples 3-15 and 3-17 to which these were not added. It can be understood that by using a high boiling point solvent (D-1) and a fluidity enhancer (F-1), the thermal fluidity of the metal-containing film-forming compound can be further improved.

[0466] [Evaluation of etching resistance]

[0467] 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 at the temperature shown in Table 7 for 60 seconds 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 7. In addition, a dry etching device TE-8500 manufactured by Tokyo Electron Co., Ltd. was used for etching.

[0468] The CF4-based gas etching conditions are as follows.

[0469]

[0470]

[0471] [Table 7]

[0472]

[0473] As shown in Table 7, it can be understood that Examples 4-1 to 4-4 using the resist metal-containing film-forming composition of the present invention, Comparative Examples 4-1 to 4-2 using similar metal-containing film-forming compositions, and Comparative Example 4-3 using the titanium compound reported in [Synthesis Example A-II] of Japanese Patent No. 6189758 Gazette, show excellent etching resistance to CF-based gas, and O2 etching resistance is better than Comparative Example 4-4 using an organic resist underlayer film material. In particular, Example 4-1 shows excellent etching resistance, which is believed to be due to the high content of tin.

[0474] [Pattern Formation Method (Examples 5-1 to 5-4, Comparative Examples 5-1 to 5-2)]

[0475] The metal-containing film-forming compositions (UDL-2, UDL-4, UDL-8 and UDL-11) with good film-forming properties after additional baking in the above solvent resistance evaluation and comparative examples UDL-5 to 6 were coated on SiO2 wafer substrates with a trench pattern (trench width 10 μm, trench depth 0.10 μm), and calcined at 250°C for 60 seconds in the atmosphere to form a metal-containing film with a thickness of 100 nm. A silicon-atom-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 30 nm, and an ArF single-layer resist material for a resist upper layer film was coated thereon and baked at 105°C for 60 seconds to form a photoresist film with a thickness of 100 nm. A wet protection film material (TC-1) was applied on the photoresist film and baked at 90° C. for 60 seconds to form a protection film with a film thickness of 50 nm.

[0476] A polymer represented by an ArF silicon-containing intermediate film polymer (SiP1) as an anti-etching intermediate layer material (SOG-1) containing silicon atoms, 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 8, and filtered through a filter material made of fluororesin with a pore size of 0.1 μm to prepare an anti-etching intermediate layer material (SOG-1) containing silicon atoms.

[0477] [Table 8]

[0478]

[0479] The structural formulas of the ArF silicon-containing intermediate film polymer (SiP1) and the crosslinking catalyst (CAT1) used are shown below.

[0480] [Chemistry 58]

[0481]

[0482] As for the resist upper 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 9, and the mixture is prepared by filtering through a filter material made of a 0.1 μm fluororesin.

[0483] [Table 9]

[0484]

[0485] 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.

[0486] [Chemistry 59]

[0487]

[0488] 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 the solution through a 0.1 μm fluororesin filter.

[0489] [Table 10]

[0490]

[0491] The polymer (PP1) used for the wet protective film material (TC-1) is shown below.

[0492] [Chemistry 60]

[0493]

[0494] 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).

[0495] Then, by dry etching, the resist pattern was 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 was used as a mask to etch the metal oxide film to form a metal oxide film pattern, and the obtained metal oxide film pattern was used as a mask to etch the SiO2 film. The etching device used was ULVAC CE-3001, and the etching conditions were as follows.

[0496] Transfer conditions of the resist pattern to the resist intermediate layer material containing silicon atoms (SOG-1).

[0497] Dry etching conditions using CF4 gas

[0498] Pressure: 1Pa

[0499] Antenna RF power: 100W

[0500] Bias RF power: 15W

[0501] CF4 gas flow rate: 15sccm

[0502] Time: 60 seconds

[0503] Transfer conditions of SOG-1 hard mask pattern to metal-containing film.

[0504] Pressure: 1Pa

[0505] Antenna RF power: 320W

[0506] Bias RF power: 30W

[0507] Cl2 gas flow rate: 25sccm

[0508] Time (Example 5-1 to Example 5-4): 15 sec

[0509] Time (Comparative Example 5-1 and Comparative Example 5-2): 60 sec

[0510] Transfer conditions of metal-containing film patterns to SiO2 films.

[0511] Dry etching conditions using CF4 gas

[0512] Pressure: 1Pa

[0513] Antenna RF power: 100W

[0514] Bias RF power: 15W

[0515] CF4 gas flow rate: 15sccm

[0516] Time: 60 seconds

[0517] Table 11 shows the results of observing the pattern cross section with an electron microscope (S-4700) manufactured by Hitachi, Ltd.

[0518] [Table 11]

[0519]

[0520] As shown in Table 11, in Examples 5-1 to 5-4 using the metal oxide film-forming composition of the present invention, the resist upper film pattern was ultimately well transferred to the substrate in any case, confirming that the metal oxide film-forming composition of the present invention can be ideally used in micro-processing by 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 planarization 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 planarization 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.

[0521] 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 forming composition having excellent dry etching resistance relative to known organic underlayer film materials and a high degree of filling / planarization properties, and is extremely useful as a resist underlayer film material used in a multilayer resist method and as a reversal agent used in a tone reversal etching method.

[0522] This manual contains the following aspects.

[0523] [1]: A metal-containing film-forming compound, which is a reaction product of a compound having two or more diol structures in its molecule and a Sn compound, wherein:

[0524] It is a monomolecular compound containing two or more Sn atoms in one molecule.

[0525] [2]: The metal-containing film-forming compound according to [1], wherein the metal-containing film-forming compound is represented by the following general formula (M-1) or (M-2);

[0526] [Chemistry 61]

[0527]

[0528] In the general formulae (M-1) to (M-2), R1 and R2 are each independently a monovalent organic group or a halogen atom; X1 is selected from a substituted or unsubstituted straight-chain alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 70 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted triazine ring, a substituted or unsubstituted isocyanuric acid, and an n1-valent organic group in a substituted or unsubstituted glycoluril group, wherein n1 is an integer of 2 to 6, and the alkyl group and the aliphatic unsaturated hydrocarbon group may also have an ether group, a thioether group, an ester group, or an amide group; R3 represents a substituent other than a hydrogen atom, and each is independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. an oxy group, 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 carboxyl group, or a halogen atom, wherein l is an integer from 0 to 1, and m1 is an integer from 0 to 5; X2 is a single bond, or a linking portion, wherein the linking portion is a carbonyl group, an ether group, an ester group, or an amide group, or is selected from a substituted or unsubstituted straight-chain alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted 2 to 2 carbon atoms containing one or more double bonds or triple bonds, 0, a substituted or unsubstituted aryl group having 6 to 36 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 36 carbon atoms, and an n2-valent organic group in a substituted or unsubstituted triazine ring, and the alkyl group and the aliphatic unsaturated hydrocarbon group may also have a keto group, an ether group, an ester group, an amide group, an imine group, a lactone ring, and a sultone ring, or a 2×n2-valent organic group in a substituted or unsubstituted saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms that forms a cyclic structure with the aromatic ring, and the hydrocarbon group may also have an ether group, and n2 is an integer from 2 to 4.

[0529] [3]: A metal-containing film-forming compound as described in [2], wherein in the general formula (M-1) to (M-2), R1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms.

[0530] [4]: The metal-containing film-forming compound according to [2] or [3], wherein R2 is -OC(=O)R2', and R2' is a monovalent organic group.

[0531] [5]: The metal-containing film-forming compound of [4], 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);

[0532] [Chemistry 62]

[0533]

[0534] 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 arylalkyl 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 arylalkyl group having 7 to 31 carbon atoms, R A1 It is an organic group represented by the following general formula (1) in which the protective group is removed 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;

[0535] [Chemistry 63]

[0536]

[0537] In the general formula (1), R A2 is an organic group whose protective group will be removed by the action of one or both of acid and heat, and * indicates that A1 or Y A2 The bond of

[0538] [Chemistry 64]

[0539]

[0540] 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;

[0541] [Chemistry 65]

[0542] B=*-Y B -R B (B)

[0543] In the general formula (B), Y Bis 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 arylalkyl 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;

[0544] [Chemistry 66]

[0545]

[0546] 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

[0547] [Chemistry 67]

[0548]

[0549] In the general formula (3), X is a divalent organic group having 1 to 31 carbon atoms, C is the following general formulas (C-1) to (C-4), and * indicates the bonding site with the carbonyl group;

[0550] [Chemistry 68]

[0551]

[0552] 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 arylalkyl group having 7 to 31 carbon atoms; * indicates the bonding site to the carbonyl group.

[0553] [6]: The metal-containing film-forming compound according to [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 a substituted or unsubstituted unsaturated hydrocarbon having 2 to 20 carbon atoms.

[0554] [7]: The metal-containing film-forming compound according to [5] or [6], 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);

[0555] [Chemistry 69]

[0556]

[0557] 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.

[0558] [8]: The metal-containing film-forming compound according to any one of [2] to [7], wherein in the general formula (M-2), m1 is 0 or 1, and when m1=1, R3 is a hydroxyl group.

[0559] [9]: A metal-containing film-forming compound as described in any one of [1] to [8], 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 measured by gel permeation chromatography is 1.00≤Mw / Mn≤1.50.

[0560]

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

[0561] Contains (a) the metal-containing film-forming compound according to any one of [1] to [9] and (b) an organic solvent.

[0562]

[11] : The metal-containing film-forming composition as described in

[10] 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.

[0563]

[12] : A metal-containing film-forming composition as described in

[10] or

[11] , 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.

[0564]

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

[0565] (I-1) a step of applying the metal-containing film-forming composition according to any one of

[10] to

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

[0566] (I-2) forming a resist upper layer film on the metal-containing film using a photoresist material;

[0567] (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;

[0568] (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

[0569] (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.

[0570]

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

[0571] (II-1) a step of applying the metal-containing film-forming composition according to any one of

[10] to

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

[0572] (II-2) a step of forming a resist intermediate film on the metal-containing film;

[0573] (II-3) forming a resist upper film on the resist intermediate film using a photoresist material;

[0574] (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;

[0575] (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;

[0576] (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

[0577] (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.

[0578]

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

[0579] (III-1) a step of applying the metal-containing film-forming composition according to any one of

[10] to

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

[0580] (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;

[0581] (III-3) forming an organic thin film on the inorganic hard mask intermediate film;

[0582] (III-4) forming a resist upper layer film on the organic thin film using a photoresist material;

[0583] (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;

[0584] (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;

[0585] (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

[0586] (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.

[0587]

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

[0588] (IV-1) forming a resist underlayer film on a substrate to be processed;

[0589] (IV-2) a step of coating the metal-containing film-forming composition as described in any one of

[10] to

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

[0590] (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;

[0591] (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;

[0592] (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;

[0593] (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

[0594] (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.

[0595]

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

[0596] (V-1) forming a resist underlayer film on a substrate to be processed;

[0597] (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;

[0598] (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;

[0599] (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;

[0600] (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;

[0601] (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;

[0602] (V-7) a step of coating a metal-containing film-forming composition as described in any one of

[10] to

[12] 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;

[0603] (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;

[0604] (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;

[0605] (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;

[0606] (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.

[0607]

[18] The pattern forming method of

[15] or

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

[0608] 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.

[0609] Description of Reference Numerals

[0610] 1: Processed substrate

[0611] 2: Processing layer

[0612] 2a: Pattern (pattern formed on the processed layer)

[0613] 3: Metal-containing resist underlayer film

[0614] 3a: Metal-containing resist lower film pattern

[0615] 4: Silicon-containing resist interlayer

[0616] 4a: Silicon-containing resist interlayer pattern

[0617] 5: Resist upper film

[0618] 5a: Resist upper film pattern

[0619] 6: Exposure part

[0620] 7: Resist underlayer film composed of coating type organic underlayer film material

[0621] 7a: Resist lower film pattern composed of coating type organic lower film material

[0622] 8:Metallic film

[0623] 8a: Metal-containing film pattern obtained by inverting the resist lower film pattern

[0624] 9: Base substrate with dense lines and spaces

[0625] 10: Metal-containing resist underlayer film

[0626] 11: Base substrate with dense lines and spaces

[0627] 12: Metal-containing resist underlayer film

[0628] Delta12: The height difference of the metal-containing resist lower layer film 12 between the pattern part and the non-pattern part.

Claims

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

2. The metal-containing film-forming compound according to claim 1, wherein The metal-containing film-forming compound is represented by the following general formula (M-1) or (M-2); In the general formulae (M-1) to (M-2), R1 and R2 are each independently a monovalent organic group or a halogen atom; X1 is selected from a substituted or unsubstituted straight-chain alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 70 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted triazine ring, a substituted or unsubstituted isocyanuric acid, and an n1-valent organic group in a substituted or unsubstituted glycoluril group, wherein n1 is an integer of 2 to 6, and the alkyl group and the aliphatic unsaturated hydrocarbon group may also have an ether group, a thioether group, an ester group, or an amide group; R3 represents a substituent other than a hydrogen atom, and each is independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. an oxy group, 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 carboxyl group, or a halogen atom, wherein l is an integer from 0 to 1, and m1 is an integer from 0 to 5; X2 is a single bond, or a linking portion, wherein the linking portion is a carbonyl group, an ether group, an ester group, or an amide group, or is selected from a substituted or unsubstituted straight-chain alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted 2 to 2 carbon atoms containing one or more double bonds or triple bonds, 0, a substituted or unsubstituted aryl group having 6 to 36 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 36 carbon atoms, and an n2-valent organic group in a substituted or unsubstituted triazine ring, and the alkyl group and the aliphatic unsaturated hydrocarbon group may also have a keto group, an ether group, an ester group, an amide group, an imine group, a lactone ring, and a sultone ring, or a 2×n2-valent organic group in a substituted or unsubstituted saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms that forms a cyclic structure with the aromatic ring, and the hydrocarbon group may also have an ether group, and n2 is an integer from 2 to 4.

3. The metal-containing film-forming compound according to claim 2, wherein In the general formulas (M-1) to (M-2), R1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms.

4. The metal-containing film-forming compound according to claim 2, wherein The R2 is -OC(=O)R2', and R2' is a monovalent organic group.

5. The metal-containing film-forming compound according to claim 4, 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 arylalkyl 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 arylalkyl group having 7 to 31 carbon atoms, R A1 It is an organic group represented by the following general formula (1) in which the protective group is removed 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 protective group will be removed by the action of one or both of acid and heat, and * indicates that 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 arylalkyl 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 the following general formulas (C-1) to (C-4), and * indicates the bonding site with 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 arylalkyl group having 7 to 31 carbon atoms; * indicates the bonding site to the carbonyl group.

6. The metal-containing film-forming compound according to claim 5, 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.

7. The metal-containing film-forming compound according to claim 5, 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.

8. The metal-containing film-forming compound according to claim 2, wherein In the general formula (M-2), m1 is 0 or 1, and when m1=1, R3 is a hydroxyl group.

9. 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 measured by gel permeation chromatography in terms of polystyrene is 1.00≤Mw / Mn≤1.

50.

10. 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 9 and (b) an organic solvent.

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

12. The metal-containing film-forming composition according to claim 10, 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.

13. 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 10 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.

14. A method for forming a pattern on a processed substrate. 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 10; (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.

15. A method for forming a pattern on a processed substrate. The method is characterized by having the following steps: (III-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 10; (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.

16. 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 applying the metal-containing film-forming composition according to claim 10 onto 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.

17. 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 10 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.

18. 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.

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

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