Metal-containing film-forming compound, metal-containing film-forming composition, method for producing metal-containing film-forming compound, 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, a method for producing a compound for forming a metal-containing film, and a pattern forming method. Provided is a metal-containing compound for forming a film, which has excellent dry etching resistance compared to known organic underlayer film materials and also has a high degree of landfill characteristics and / or a high degree of planarization characteristics. A metal-containing film-forming compound (A) is a metal-containing film-forming compound which is derived from a metal-containing compound obtained by hydrolyzing, condensing, or hydrolytically condensing a metal compound represented by formula (A-1), and which has a ligand derived from an organic compound represented by formula (1). M (OR1A) 4 (A-1), R2ACOXCOOH (1) # imgabs0 #

Description

Technical Field

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

[0002] With the high integration and high speed of LSI, the miniaturization of pattern size is progressing rapidly. With this miniaturization, photolithography technology has achieved the formation of fine patterns by shortening the wavelength of the light source and appropriately selecting the corresponding resist composition. The core of this is the positive photoresist composition used in a single layer. This single-layer positive photoresist composition has a skeleton with etching resistance to dry etching using chlorine-based or fluorine-based gas plasma in the resist resin and a switching mechanism that dissolves the exposed part, thereby dissolving the exposed part to form a pattern, and using the remaining resist pattern as an etching mask to dry etch the substrate to be processed.

[0003] However, if the thickness of the photoresist film used is directly miniaturized, that is, if the pattern width is further reduced, the resolution performance of the photoresist film will be reduced, and if the photoresist film is to be patterned using a developer, the so-called aspect ratio will become too large, resulting in a problem of pattern collapse. Therefore, as the pattern becomes miniaturized, the photoresist film will become thinner and thinner.

[0004] On the other hand, the processing of the processed substrate usually uses a method of processing the substrate by dry etching using a patterned photoresist film as an etching mask, but in reality there is no dry etching method that can obtain complete etching selectivity between the photoresist film and the processed substrate. Therefore, in the substrate processing, there will be a problem that even the photoresist film is damaged and collapsed, and the resist pattern cannot be correctly transferred to the processed substrate. With the miniaturization of the pattern, higher dry etching resistance is required for the resist composition. However, on the other hand, in order to improve the resolution, the resin used in the photoresist composition is increasingly required to have a small light absorption at the exposure wavelength. Therefore, as the exposure light progresses to the shorter wavelength of i-rays, KrF, and ArF, the resin also changes to novolac resin, polyhydroxystyrene, and resin with an aliphatic polycyclic skeleton. However, in reality, the etching speed of the dry etching conditions during substrate processing becomes faster, and the recent photoresist composition with high resolution tends to weaken the etching resistance instead.

[0005] Therefore, the substrate to be processed must be dry-etched with a thinner photoresist film with weaker etching resistance, and ensuring the materials and processing in this processing step becomes a top priority.

[0006] One method for solving such a problem is a multilayer resist method. In this method, a resist intermediate film having a different etching selectivity from the photoresist film (i.e., the resist upper film) is inserted between the resist upper film and the substrate to be processed. After the resist upper film has a pattern, the resist upper film pattern is used as a dry etching mask to transfer the pattern to the resist lower film by dry etching, and then the resist lower film is used as a dry etching mask to transfer the pattern to the substrate to be processed by dry etching.

[0007] One of the multilayer resist methods is a three-layer resist method that can be implemented using a general resist composition used in the single-layer resist method. In this three-layer resist method, for example, an organic film obtained from a novolac resin or the like is formed on a substrate to be processed as a resist lower film, a silicon-containing film is formed thereon as a silicon-containing resist intermediate film, and a normal organic photoresist film is formed thereon as a resist upper film. When dry etching is performed using fluorine-based gas plasma, the organic resist upper film can achieve a good etching selectivity ratio with respect to the silicon-containing resist intermediate film, and therefore, the resist upper film pattern can be transferred to the silicon-containing resist intermediate film by dry etching using fluorine-based gas plasma. According to this method, even when a resist composition that is difficult to form a pattern with a sufficient film thickness for a substrate to be directly processed is used, or a resist composition that does not have sufficient dry etching resistance for substrate processing is used, if the pattern can be transferred to a silicon-containing resist intermediate film (resist intermediate film), and then the pattern transfer is performed by dry etching using oxygen or hydrogen gas plasma, a pattern of an organic film (resist underlayer film) made of novolac resin or the like having sufficient dry etching resistance for substrate processing can be obtained. As for the above-mentioned resist underlayer film, many are known, such as those described in Patent Document 1.

[0008] On the other hand, in recent years, the miniaturization of DRAM memory has accelerated, and the need for a resist underlayer film with improved dry etching resistance and excellent filling and planarization characteristics has increased. There have been reports of coating-type organic underlayer film materials with excellent filling and planarization characteristics, such as those described in Patent Document 2, but when it is expected to be used in the advanced generation, there are concerns about dry etching resistance, and the applicability limit of known coating-type organic underlayer film materials has been approached.

[0009] In view of the above problems, some people have studied the development of materials containing metal elements for use in resist underlayer films. Patent Document 3 reports that materials using Ti compounds show excellent dry etching resistance to CHF3 / CF4 gas and CO2 / N2 gas.

[0010] On the other hand, there are issues when metal compounds are used in resist underlayer films, such as embedding properties. Patent document 3 does not mention embedding properties, but in general, metal oxide compounds have large thermal shrinkage during baking, and high-temperature baking will induce significant degradation of the filling properties, so there are concerns that they are not ideal as resist underlayer film materials that require high levels of flattening properties, embedding properties, and heat resistance. Patent documents 4 and 5 report that metal compounds modified with specific ligands have excellent embedding properties, but the firing temperature for the embedding property evaluation is a low temperature of 150°C, which is not ideal for resist underlayer films that require heat resistance (for example: properties for heat treatment that is sometimes performed after the formation of the resist underlayer film). In addition, because a metal compound whose hydrolyzable group is protected by a silicon-containing organic group is used, it is not easy to promote the condensation reaction, and there are concerns that the metal film obtained during firing will not be dense enough and dry etching resistance will not be enough.

[0011] As a method for improving the embedding property, it is conceivable to use a ligand with excellent thermal curing properties. Patent Document 6 reports that a metal compound having a substituted or unsubstituted vinyl group or a substituted or unsubstituted acetylene group has excellent thermal curing properties and excellent resolution and sensitivity as a radiation-sensitive composition. Examples include metal compounds with ligands derived from 4-vinylbenzoic acid and 4-allyloxybenzoic acid. However, there is still a concern that it is not ideal for resist underlayer film materials that require high heat resistance for resist materials.

[0012] Prior art literature

[0013] Patent Literature

[0014] [Patent Document 1] Japanese Patent Application Publication No. 2004-205685

[0015] [Patent Document 2] Japanese Patent No. 6714493

[0016] [Patent Document 3] Japanese Patent No. 6189758

[0017] [Patent Document 4] Japanese Patent No. 6786391

[0018] [Patent Document 5] Japanese Patent No. 7050137

[0019] [Patent Document 6] Japanese Patent Application Publication No. 2020-201480 Summary of the invention

[0020] [Problems to be solved by the invention]

[0021] In view of the above situation, the present invention aims to provide a metal-containing compound for film formation which has excellent dry etching resistance compared to known organic lower layer film materials and has a high degree of filling characteristics and / or a high degree of flattening characteristics, a method for manufacturing the compound, a metal-containing film formation composition containing the compound, and a pattern forming method using the composition.

[0022] [Methods for solving problems]

[0023] In order to solve the above-mentioned problems, the present invention provides a metal-containing film-forming compound, which is (A) a metal-containing film-forming compound,

[0024] The (A) metal-containing film-forming compound is a compound derived from a metal-containing compound obtained by hydrolyzing or condensing a metal compound represented by the following formula (A-1), or by hydrolyzing and condensing the metal compound, and has a ligand derived from an organic compound represented by the following formula (1).

[0025] M(OR 1A )4(A-1)

[0026] R 2A COXCOOH(1)

[0027] Wherein, M is Ti, Zr, or Hf, R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A It is a divalent organic group having 2 to 20 carbon atoms and containing at least one crosslinking group represented by any of the following general formulae (a-1) to (a-4), and X is a divalent organic group having 2 to 20 carbon atoms.

[0028] [Chemistry 1]

[0029]

[0030] In the above general formulas (a-1) to (a-4), R a is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding portion.

[0031] If such a metal-containing film-forming compound contains a ligand derived from an organic compound of formula (1) containing at least one crosslinking group represented by any one of (a-1) to (a-4), when it is used in a metal-containing film-forming composition, it can provide a metal-containing film-forming composition that has a small volume shrinkage during baking and has excellent flattening characteristics and / or filling characteristics even after high-temperature baking. In addition, it is a compound derived from a metal-containing compound obtained by hydrolyzing or condensing a metal compound represented by formula (A-1), or hydrolyzing and condensing it, so when it is used in a metal-containing film-forming composition, a dense metal-containing film can be formed, and a metal-containing film with extremely excellent dry etching resistance to a processed substrate can be provided.

[0032] The aforementioned (A) metal-containing compound for film formation is preferably a metal-containing compound selected from the reaction product of one or more of a hydrolyzate of a metal compound represented only by the aforementioned formula (A-1), a condensate of a metal compound represented only by the aforementioned formula (A-1), and a hydrolysis-condensation product of a metal compound represented only by the aforementioned formula (A-1), and an organic compound represented by the aforementioned formula (1).

[0033] Since such a metal-containing film-forming compound can efficiently introduce ligands from the organic compound of formula (1) into the metal compound, when used in a metal-containing film-forming composition, a metal-containing film having both high filling properties and dry etching resistance can be provided.

[0034] In the above formula (1), R 2A The structure represented by the following general formula (B-1) is preferred.

[0035] [Chemistry 2]

[0036]

[0037] In the above general formula (B-1), R A1 is the structure represented by the above general formula (a-1), R A2 is any of the structures represented by the above general formula (a-2) or (a-3), Z is an oxygen atom or a secondary amine, L is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R A3 It is a saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, t is 1 to 6, s is 0 to 5, t+s is 1 to 6, r is 1 to 10, u is 0 or 1, m is 0 or 1, and * represents a bond to the carbon atom of the carbonyl group.

[0038] In the above general formula (1), if R 2AThe structure represented by the above formula (B-1) can take into account the thermal fluidity and thermal curing properties of the above-mentioned metal-containing film-forming compound to a high degree. When it is used in a metal-containing film-forming composition, it can provide a metal-containing film-forming composition that exhibits better planarization characteristics and / or filling characteristics.

[0039] In the above formula (1), the above organic group X is preferably a saturated hydrocarbon group having 2 to 20 carbon atoms or an unsaturated hydrocarbon group having 2 to 20 carbon atoms.

[0040] In the above formula (1), if the organic group X has such a structure, the thermal fluidity of the above-mentioned metal-containing film-forming compound can be further improved. When it is used in a metal-containing film-forming composition, it can provide a metal-containing film-forming composition that exhibits better planarization characteristics and / or filling characteristics.

[0041] In the above formula (1), the above organic group X is preferably a group represented by any of the following formulas (2).

[0042] [Chemistry 3]

[0043]

[0044] In the above general formula (2), R a and R b is a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, R c is a hydrogen atom or a monovalent organic group having 1 to 17 carbon atoms, R a and R b They may be bonded to form a cyclic substituent. *1 and *2 each represent a bond to the carbonyl group, and *1 and *2 may be reversed.

[0045] In the above formula (1), if the organic group X has such a structure, the thermal fluidity of the above-mentioned metal-containing film-forming compound can be further improved. When it is used in a metal-containing film-forming composition, it can provide a metal-containing film-forming composition showing better planarization characteristics and / or filling characteristics.

[0046] For example, the metal-containing film-forming compound (A) may contain a compound having a structure represented by the following general formula (m-1).

[0047] [Chemistry 4]

[0048]

[0049] In the above formula (m-1), R ae ~R de Each independently represents R in the above formula (A-1) 1A Or COXCOR in the above formula (1) 2A Any one of Rae ~R de At least one of them is COXCOR in the above formula (1) 2A , n is 1 to 20, and M is the same as M in the above formula (A-1).

[0050] (A) The metal-containing film-forming compound is not limited, and may contain, for example, a compound having the above-mentioned structure.

[0051] The aforementioned (A) metal-containing film-forming compound preferably contains, in addition to the ligands derived from the organic compound represented by the aforementioned formula (1), at least one additional ligand selected from the ligands derived from the organic compound represented by the following formula (3) and the ligands derived from any of succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride. It is preferred that the aforementioned additional ligands do not contain the groups represented by the aforementioned general formulas (a-1) to (a-4).

[0052] R 3A COOH(3)

[0053] In the formula, R 3A It is a monovalent organic group having 1 to 20 carbon atoms.

[0054] When such a compound is used in a metal-containing film-forming composition, it can promote a crosslinking reaction during firing, and the firing temperature can be low. In addition, by promoting the crosslinking reaction, a dense metal-containing film can be formed, and etching resistance can be improved.

[0055] In this case, for example, the metal-containing film-forming compound (A) may include a compound having any one of the structures shown below.

[0056] [Chemistry 5]

[0057]

[0058] The above R 3a is a monovalent organic group having 1 to 20 carbon atoms and not containing a crosslinking group represented by the above general formulae (a-1) to (a-4), or any of the following structures, R 1A Same as R in the above formula (A-1) 1A , R 2A Same as R in formula (1) 2A , n is 1 to 20, and M is the same as M in the above formula (A-1).

[0059] [Chemistry 6]

[0060]

[0061] In the above formula, R 3bIt is an alkyl group having 1 to 10 carbon atoms, and * represents a bonding portion to the carbonyl carbon.

[0062] When an additional ligand is contained, the (A) metal-containing film-forming compound is not limited, and may contain, for example, a compound having the above-mentioned structure.

[0063] The present invention also provides a metal-containing film-forming composition, characterized in that it contains:

[0064] (A) The metal-containing film-forming compound of the present invention and

[0065] (B) Organic solvent.

[0066] If it is such a metal-containing film-forming composition, since it contains a metal-containing compound with excellent heat resistance and thermal fluidity, it can provide a metal-containing film-forming composition with excellent dry etching resistance compared to known organic lower layer film materials, and compared to known metal-containing lower layer film materials, it has a high degree of filling characteristics and / or a high degree of flattening characteristics.

[0067] The aforementioned composition may further contain

[0068] (C) a cross-linking agent,

[0069] (D) surfactant, and

[0070] (E) Acid generator

[0071] One or more of the following.

[0072] If the metal-containing film-forming composition contains the above-mentioned additive, the metal-containing film-forming composition can be more excellent in coating properties, dry etching resistance, and filling and / or planarization properties.

[0073] The (B) organic solvent contains (B-1) a high boiling point solvent, and the (B-1) high boiling point solvent is preferably one or more organic solvents having a boiling point of 180 degrees or higher.

[0074] By adding a high boiling point solvent to the metal-containing film-forming compound to impart thermal fluidity, the metal-containing film-forming composition can achieve higher levels of filling and / or planarizing properties.

[0075] The metal-containing film-forming composition preferably further contains a fluidity promoter (BP) having an organic group represented by the following general formula (bp1a) and an aromatic ring.

[0076] [Chemistry 7]

[0077]

[0078] In the formula, * represents the bonding site to the oxygen atom, R Bis a divalent organic group having 1 to 10 carbon atoms, R A It is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.

[0079] By adding a fluidity promoter (BP) to the metal-containing film-forming compound to impart heat resistance and thermal fluidity, the metal-containing film-forming composition can have a higher degree of both filling property and / or planarization property.

[0080] The fluidity improving agent (BP) preferably has at least one structural unit represented by any of the following general formulae (BP-1), (BP-2), (BP-3), (BP-4) and (BP-5).

[0081] [Chemistry 8]

[0082]

[0083] In the above general formulae (BP-1) and (BP-2), W1 and W2 are each independently a benzene ring or a naphthalene ring, and the hydrogen atoms in the benzene ring and the naphthalene ring may be substituted by a hydrocarbon group having 1 to 6 carbon atoms. a1 is a group represented by the following general formula (4). Y is a group represented by the following general formula (5). n1 is 0 or 1, n2 is 1 or 2, and V each independently represents a hydrogen atom or a linking part.

[0084] [Chemistry 9]

[0085]

[0086] In the above general formula (BP-3), Z1 is a group represented by the following general formula (6), R a1 It is the following general formula (4): n4 is 0 or 1, n5 is 1 or 2, and V each independently represents a hydrogen atom or a linking part.

[0087] [Chemistry 10]

[0088]

[0089] * indicates a bonding portion with an oxygen atom.

[0090] [Chemistry 11]

[0091]

[0092] * indicates an atomic bond.

[0093] [Chemistry 12]

[0094]

[0095] In the above general formula (6), W1, W2, Y and n1 are the same as described above.

[0096] [Chemistry 13]

[0097]

[0098] In the formula, m3 and m4 represent 1 or 2, and Z2 represents a single bond or any of the structures represented by the following general formula (7). x It is any of the structures represented by the following general formula (8).

[0099] [Chemistry 14]

[0100]

[0101] In the formula, * represents an atomic bond, l represents an integer from 0 to 3, and R az ~R fz Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with fluorine, a phenyl group, or a phenylethyl group, and R az With R bz They can also form cyclic compounds.

[0102] [Chemistry 15]

[0103]

[0104] In the formula, * represents a bonding site to an aromatic ring, and Q1 is a linear saturated hydrocarbon group having 1 to 30 carbon atoms, or a structure represented by the following general formula (9).

[0105] [Chemistry 16]

[0106]

[0107] In the formula, * represents the bonding site to the carbonyl group, R i It is the above general formula (4). j It represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. 3z and n 4z represents the number of substituents on the aromatic ring, and each represents an integer from 0 to 7. 3z +n 4z It is between 0 and 7. 5z Represents 0 to 2.

[0108] [Chemistry 17]

[0109]

[0110] In the above general formula (BP-5), R 1is a saturated monovalent organic group having 1 to 30 carbon atoms or an unsaturated monovalent organic group having 2 to 30 carbon atoms, X1 is a divalent organic group having 1 to 30 carbon atoms, R a1 In the above general formula (4), p is an integer of 0 to 5, q1 is an integer of 1 to 6, p+q1 is an integer of 1 to 6, and q2 is 0 or 1.

[0111] If the metal-containing film-forming composition to which the fluidity improving agent (BP) having at least one of the structural units represented by (BP-1) to (BP-5) is added, the metal-containing film-forming composition will have more excellent filling and / or planarizing properties.

[0112] The present invention also provides a method for producing (A) a metal-containing film-forming compound, which comprises the following steps:

[0113] reacting an organic compound represented by the following formula (1) with one or more selected from a hydrolyzate of a metal compound represented by the following formula (A-1), a condensate of a metal compound represented by the following formula (A-1), and a hydrolysis-condensate of a metal compound represented by the following formula (A-1) or more thereof; or

[0114] The metal compound represented by the following general formula (A-2) is hydrolyzed or condensed, or hydrolyzed and condensed.

[0115] M(OR 1A )4 (A-1)

[0116] R 2A COXCOOH (1)

[0117] Wherein, M is Ti, Zr, or Hf, R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A It is a divalent organic group having 2 to 20 carbon atoms and containing at least one crosslinking group represented by any of the following general formulae (a-1) to (a-4), and X is a divalent organic group having 2 to 20 carbon atoms.

[0118] [Chemistry 18]

[0119]

[0120] In the above general formulas (a-1) to (a-4), R a is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding portion.

[0121] (R 2A COXCOO x M(OR 1A ) y (A-2)

[0122] Wherein, M is Ti, Zr, or Hf, R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A It is a divalent organic group having 2 to 20 carbon atoms and containing at least one crosslinking group represented by the above general formulae (a-1) to (a-4), X is a divalent organic group having 2 to 20 carbon atoms, x+y=4, and x and y are integers greater than 1.

[0123] According to such a manufacturing method, a metal-containing film-forming compound containing a ligand derived from an organic compound of formula (1) containing any one or more of the crosslinking groups represented by any of (a-1) to (a-4) can be provided. Therefore, when the compound is used in a metal-containing film-forming composition, a metal-containing film-forming composition having a small volume shrinkage during baking and excellent flattening characteristics and / or filling characteristics even after high-temperature baking can be provided. In addition, a compound derived from a metal-containing compound obtained by hydrolyzing or condensing a metal compound represented by formula (A-1), or hydrolyzing and condensing, can be provided. When the compound is used in a metal-containing film-forming composition, a dense metal-containing film can be formed, and a metal-containing film having extremely excellent dry etching resistance to a processed substrate can be provided.

[0124] 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:

[0125] (I-1) After applying the metal-containing film-forming composition of the present invention on a substrate to be processed, a metal-containing film is formed by heat treatment,

[0126] (I-2) forming a resist upper layer film on the aforementioned metal-containing film using a photoresist material,

[0127] (I-3) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0128] (I-4) using the patterned resist upper layer film as a mask to dry-etch the metal-containing film to transfer the pattern, and

[0129] (I-5) The substrate to be processed is processed using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0130] By using the pattern forming method using the above-mentioned two-layer resist process, a fine pattern can be formed on a workpiece (workpiece substrate).

[0131] 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:

[0132] (II-1) After applying the metal-containing film-forming composition of the present invention on a substrate to be processed, a metal-containing film is formed by heat treatment.

[0133] (II-2) forming a resist intermediate film on the aforementioned metal-containing film,

[0134] (II-3) forming a resist upper layer film on the resist intermediate film using a photoresist material,

[0135] (II-4) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0136] (II-5) using the patterned resist upper layer film as a mask, dry etching is performed to transfer the pattern to the resist intermediate layer film,

[0137] (II-6) using the resist intermediate film having the transferred pattern as a mask, dry etching the transferred pattern on the metal-containing film, and

[0138] (II-7) The substrate to be processed is processed using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0139] By using the pattern forming method using the three-layer resist process described above, a fine pattern can be formed on a workpiece with high precision.

[0140] 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:

[0141] (III-1) After applying the metal-containing film-forming composition of the present invention on a substrate to be processed, a metal-containing film is formed by heat treatment.

[0142] (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 aforementioned metal-containing film,

[0143] (III-3) forming an organic thin film on the aforementioned inorganic hard mask intermediate film,

[0144] (III-4) forming a resist upper layer film on the aforementioned organic thin film using a photoresist material,

[0145] (III-5) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0146] (III-6) using the patterned resist upper layer film as a mask, dry etching is performed to transfer the pattern to the organic thin film and the inorganic hard mask intermediate film,

[0147] (III-7) using the inorganic hard mask intermediate film having the transferred pattern as a mask, dry etching the transferred pattern on the metal-containing film, and

[0148] (III-8) The substrate to be processed is processed using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0149] By using the pattern forming method using the above-mentioned four-layer resist process, a fine pattern can be formed on a workpiece with high precision.

[0150] At this time, the inorganic hard mask intermediate film is preferably formed by a CVD method or an ALD method.

[0151] When the inorganic hard mask is formed by a CVD method or an ALD method, a fine pattern can be formed on a workpiece with higher precision.

[0152] 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:

[0153] (IV-1) After applying the metal-containing film-forming composition of the present invention on a substrate to be processed, a metal-containing film is formed by heat treatment.

[0154] (IV-2) forming an organic intermediate film on the aforementioned metal-containing film,

[0155] (IV-3) forming a combination of an inorganic hard mask interlayer film selected from a resist interlayer film containing silicon or a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film and an organic thin film on the aforementioned organic interlayer film,

[0156] (IV-4) forming a resist upper layer film using a photoresist material on the aforementioned silicon-containing resist intermediate film or the aforementioned organic thin film,

[0157] (IV-5) after pattern-exposing the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0158] (IV-6) using the patterned resist upper layer film as a mask, dry etching is performed to transfer the pattern to the silicon-containing resist intermediate film or the organic thin film and the inorganic hard mask intermediate film,

[0159] (IV-7) using the silicon-containing resist intermediate film or inorganic hard mask intermediate film to which the pattern has been transferred as a mask, and dry etching the pattern transferred on the organic intermediate film,

[0160] (IV-8) using the organic intermediate film having the transferred pattern as a mask to dry-etch the transferred pattern on the metal-containing film, and

[0161] (IV-9) The substrate to be processed is processed using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0162] The pattern forming method using the multilayer resist process described above can form a fine pattern on a workpiece with high precision.

[0163] Furthermore, the present invention provides a tonality reversal pattern forming method, which is a method for forming a pattern on a processed substrate, characterized by having the following steps:

[0164] (V-1) forming a resist underlayer film on a substrate to be processed,

[0165] (V-2) forming a resist intermediate film, or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film and an organic thin film on the resist underlayer film,

[0166] (V-3) forming a resist upper layer film using a photoresist material on the aforementioned resist intermediate film or the combination of the inorganic hard mask intermediate film and the organic thin film,

[0167] (V-4) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0168] (V-5) using the patterned resist upper layer film as a mask, dry etching to transfer a pattern to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film,

[0169] (V-6) using the resist intermediate film or inorganic hard mask intermediate film to which the pattern has been transferred as a mask, dry etching is performed to transfer the pattern on the resist lower layer film,

[0170] (V-7) coating the metal-containing film-forming composition of the present invention on the aforementioned patterned resist underlayer film, and then covering the metal-containing film by heat treatment to fill the space between the patterns of the aforementioned resist underlayer film with the aforementioned metal-containing film,

[0171] (V-8) etching back the metal-containing film on the resist underlayer film having the pattern formed thereon by chemical stripping agent or dry etching to expose the top surface of the resist underlayer film having the pattern formed thereon,

[0172] (V-9) the resist intermediate film or the hard mask intermediate film remaining on the top surface of the resist lower layer film is removed by dry etching,

[0173] (V-10) removing the aforementioned patterned resist underlayer film exposed on the surface by dry etching to form a reverse pattern of the original pattern on the metal-containing film,

[0174] (V-11) The metal-containing film having the reverse pattern formed therein is used as a mask to process the substrate to be processed, thereby forming a reverse pattern on the substrate to be processed.

[0175] By using the pattern forming method using the above-mentioned inversion process, a fine pattern can be formed on the workpiece with higher precision.

[0176] [Effects of the Invention]

[0177] As described above, among the metal-containing film-forming compounds of the present invention, the aforementioned metal-containing film-forming compounds are compounds derived from the metal compounds represented by the above formula (A-1) being hydrolyzed or condensed, or the metal-containing compounds being obtained by hydrolysis and condensation, and further, are metal-containing film-forming compounds having ligands derived from the organic compound represented by the above formula (1). Therefore, when it is used in a metal-containing film-forming composition, it is possible to provide a metal-containing film-forming composition having small volume shrinkage during baking and having excellent flattening characteristics and / or filling characteristics after high-temperature baking.

[0178] In particular, in the fine patterning process using the multilayer resist method in the semiconductor device manufacturing step, even on the processed substrate with a dense portion of a fine pattern structure with a high aspect ratio, such as a DRAM memory with progressive miniaturization, which is difficult to fill and / or flatten, the metal-containing film-forming composition containing the metal-containing film-forming compound of the present invention can still be filled without causing defects such as pores and peeling, and has excellent dry etching resistance compared to known coating-type resist underlayer materials, so compared with known resist underlayer films, it is possible to form a fine pattern on the processed body with higher precision.

[0179] Furthermore, if it is a method for producing a metal-containing film-forming compound of the present invention, it is possible to produce a metal-containing film-forming compound obtained by hydrolyzing or condensing the metal compound represented by the above formula (A-1), or by hydrolyzing and condensing the metal compound and having a ligand from the organic compound represented by the above formula (1). Therefore, when it is used in a metal-containing film-forming composition, it can provide a metal-containing film-forming composition with small volume shrinkage during baking and excellent flattening characteristics and / or filling characteristics even after high-temperature baking.

[0180] The pattern forming method of the present invention can form a fine pattern on a workpiece with higher precision by using the metal-containing film-forming composition of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0181] Figure 1 (A) to (F) are explanatory diagrams of an example (three-layer resist process) of the pattern forming method of the present invention.

[0182] Figure 2 (G) to (P) are explanatory diagrams of an example of the tone reversal pattern forming method of the present invention (reversal of the SOC pattern in the three-layer resist process).

[0183] Figure 3 (Q) to (S) are explanatory diagrams of the landfill characteristic evaluation method.

[0184] Figure 4 (T) and (U) are explanatory diagrams of the planarization characteristic evaluation method. DETAILED DESCRIPTION

[0185] As described above, the present invention seeks to develop a metal-containing film-forming composition having excellent filling properties and flatness for use in forming a metal-containing film that can transfer a resist pattern to a processed substrate with higher precision in a fine patterning process using a multilayer resist method, a metal-containing film-forming compound useful for the composition, and a pattern forming method using the aforementioned composition.

[0186] The inventors of the present application have focused on metal materials that show excellent etching resistance in comparison with known resist lower film materials and have made great efforts to study them. On the other hand, the metal compounds used to form known resist lower film lack heat resistance and cause severe volume shrinkage when baked, 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 have considered that if there is an organic group with excellent heat resistance, the severe volume shrinkage during baking can be reduced, the thermal fluidity can be improved, and the height difference of the processed substrate can be filled without pores after high-temperature baking. Furthermore, if it is a structure containing a cross-linking group at the end, the thermal curing property during baking is excellent, and it is speculated that it will become a metal-containing film-forming compound with better heat resistance. Furthermore, there is a concern that the dry etching resistance of the metal-containing film may deteriorate by introducing organic ligands with excellent heat resistance. Therefore, the inventors of the present application speculate that by using a compound derived from a metal compound that is hydrolyzed or condensed, or a metal-containing compound obtained by hydrolysis and condensation, the dry etching resistance can be improved without deteriorating the filling characteristics.

[0187] The inventors of the present case have made further efforts to explore and found that if the compound is a metal-containing compound obtained by hydrolyzing or condensing a metal compound represented by the following formula (A-1), or by hydrolysis and condensation, and contains a metal-containing compound for forming a film containing ligands from an organic compound represented by formula (1) containing any one or more cross-linking groups represented by (a-1) to (a-4), then it has excellent thermal curing properties, so it can reduce the drastic volume shrinkage during baking, and the thermal fluidity is also good, so it can provide a resist underlayer film that achieves a high degree of filling characteristics and / or a high degree of flattening characteristics and has excellent dry etching resistance, thereby completing the present invention.

[0188] That is, the present invention is a metal-containing film-forming compound, which is (A) a metal-containing film-forming compound, characterized in that:

[0189] The aforementioned (A) metal-containing film-forming compound is a compound derived from a metal-containing compound obtained by hydrolyzing or condensing a metal compound represented by the following formula (A-1), or by hydrolyzing and condensing the metal compound, and has a ligand derived from an organic compound represented by the following formula (1).

[0190] M(OR 1A )4(A-1)

[0191] R 2A COXCOOH(1)

[0192] Wherein, M is Ti, Zr, or Hf, R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A It is a divalent organic group having 2 to 20 carbon atoms and containing at least one crosslinking group represented by any of the following general formulae (a-1) to (a-4), and X is a divalent organic group having 2 to 20 carbon atoms.

[0193] [Chemistry 19]

[0194]

[0195] In the above general formulas (a-1) to (a-4), R a is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding portion.

[0196] The present invention is described in detail below, but the present invention is not limited thereto.

[0197] <(A) Metal-Containing Film-Forming Compound>

[0198] The (A) metal-containing film-forming compound of the present invention is a metal-containing film-forming compound, which is a metal-containing compound obtained by hydrolyzing or condensing a metal compound represented by the following formula (A-1), or by hydrolysis and condensation, and further has a ligand from an organic compound represented by the following formula (1).

[0199] M(OR 1A )4 (A-1)

[0200] R 2A COXCOOH (1)

[0201] Wherein, M is Ti, Zr, or Hf, R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2AIt is a divalent organic group having 2 to 20 carbon atoms and containing at least one crosslinking group represented by any of the following general formulae (a-1) to (a-4), and X is a divalent organic group having 2 to 20 carbon atoms.

[0202] [Chemistry 20]

[0203]

[0204] In the above general formulas (a-1) to (a-4), R a is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding portion.

[0205] If the compound is derived from a metal-containing compound obtained by hydrolyzing or condensing a metal compound, or hydrolyzing and condensing a metal compound, it has at least one [metal]-[oxygen]-[metal] bond, and when it is used to form a metal-containing film, a metal-containing film with high hardness and excellent density can be provided. In addition, by hydrolyzing or condensing, or hydrolyzing and condensing during the synthesis of the compound, the volume shrinkage accompanying the condensation reaction during the film firing can be reduced, so that the landfill characteristics can be further improved.

[0206] In the above formula (A-1), R 1A It is a monovalent organic group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an isopropyl group or an n-butyl group from the viewpoint of productivity of the metal compound.

[0207] Examples of the metal compound represented by the above formula (A-1) include tetraisopropoxytitanium, butoxytitanium tetramer, tetrabutoxyzirconium (IV), n-butoxyhafnium (IV), tetraisopropoxyzirconium (IV), and tetrapropoxyzirconium (IV).

[0208] In the above formula (1), R 2A It is a divalent organic group having 2 to 20 carbon atoms and containing at least one crosslinking group represented by any of the general formulae (a-1) to (a-4).

[0209] By having ligands from such organic compounds, the thermal curing property of the (A) metal-containing film-forming compound is improved, and when used in a metal-containing film-forming composition, it can provide a metal-containing film-forming composition that can reduce volume shrinkage during high-temperature baking and has excellent filling and / or flattening properties.

[0210] In the above (a-1) to (a-4), R a It is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. In view of the availability of raw materials, a hydrogen atom, a methyl group or a phenyl group is preferred. In view of the thermosetting property, a hydrogen atom is more preferred.

[0211] The aforementioned (A) metal-containing compound for film formation is preferably a metal-containing compound selected from the hydrolyzate of the metal compound represented by the aforementioned formula (A-1), the condensate of the metal compound represented only by the aforementioned formula (A-1), and one or more hydrolysis-condensation products of the metal compound represented only by the aforementioned formula (A-1), and the reaction product of an organic compound represented by the aforementioned formula (1).

[0212] Such a metal-containing film-forming compound can efficiently introduce ligands from the organic compound of formula (1) into the metal compound. Therefore, when used in a metal-containing film-forming composition, it can provide a metal-containing film having both high filling properties and dry etching resistance.

[0213] In the above formula (1), R 2A The structure represented by the following general formula (B-1) is preferred.

[0214] [Chemistry 21]

[0215]

[0216] In the above general formula (B-1), R A1 is the structure represented by the above general formula (a-1), R A2 is any of the structures represented by the above general formula (a-2) or (a-3), Z is an oxygen atom or a secondary amine, L is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R A3 It is a saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, t is 1 to 6, s is 0 to 5, t+s is 1 to 6, r is 1 to 10, u is 0 or 1, m is 0 or 1, and * represents a bond to the carbon atom of the carbonyl group.

[0217] In the above general formula (B-1), r is 1 to 10, t is 1 to 6, s is 0 to 5, t+s is 1 to 6, u is 0 or 1, and m is preferably 0 or 1. When m is 1, L is preferably a methylene group. A more preferred structure is one in which r is 1 to 4, t is 1 to 2, s is 0 to 1, and m is 0.

[0218] In the above formula (1), R 2A If the structure is represented by the general formula (B-1), the thermal fluidity and thermal curing properties of the metal-containing film-forming compound (A) can be further improved. When used in a metal-containing film-forming composition, a metal-containing film-forming composition having better planarization properties and / or filling properties can be provided.

[0219] In the above formula (1), the above organic group X is preferably a saturated hydrocarbon group having 2 to 20 carbon atoms or an unsaturated hydrocarbon group having 2 to 20 carbon atoms.

[0220] With such a structure, the thermal fluidity of the metal-containing film-forming compound (A) can be further improved. When used in the metal-containing film-forming composition (A), a metal-containing film-forming composition having better planarization characteristics and / or filling characteristics can be provided.

[0221] In the above formula (1), the above organic group X is preferably a group represented by any of the following formulas (2).

[0222] [Chemistry 22]

[0223]

[0224] In the above general formula (2), R a and R b is a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, R c is a hydrogen atom or a monovalent organic group having 1 to 17 carbon atoms, R a and R b They may be bonded to form a cyclic substituent. *1 and *2 each represent a bond to the carbonyl group, and *1 and *2 may be reversed.

[0225] In the above formula (1), if the organic group X has such a structure, the thermal fluidity of the above metal-containing film-forming compound (A) can be further improved. And when it is used in a metal-containing film-forming composition, a metal-containing film-forming composition showing better planarization characteristics and / or filling characteristics can be provided.

[0226] Examples of the preferred structures of the above formula (1) include the following compounds, but the present invention is not limited to these.

[0227] [Chemistry 23]

[0228]

[0229] [Chemistry 24]

[0230]

[0231] From the viewpoint of landfill properties, in the above formula (B-1), Z is more preferably a secondary amine.

[0232] The above-mentioned (A) metal-containing film-forming compound may contain one or more ligands of different structures derived from the organic compound represented by the above formula (1), and may be appropriately adjusted in accordance with the necessary properties required when using the metal-containing film-forming composition. In addition, it may also contain ligands other than the ligands derived from the organic compound represented by the above formula (1). For example, it may contain ligands derived from an alkyl group having 1 to 10 carbon atoms.

[0233] (A) The metal-containing film-forming compound preferably contains a compound having a structure represented by the following general formula (m-1).

[0234] [Chemistry 25]

[0235]

[0236] In the above formula (m-1), R ae ~R de Each independently represents R in the above formula (A-1) 1A Or COXCOR in the above formula (1) 2A Any one of R ae ~R de At least one of them is COXCOR in the above formula (1) 2A , n is 1 to 20, and M is the same as M in the above formula (A-1).

[0237] The aforementioned (A) metal-containing film-forming compound is a compound derived from a metal-containing compound obtained by hydrolyzing or condensing the metal compound represented by the aforementioned formula (A-1), or by hydrolyzing and condensing the metal compound. In addition to the ligands derived from the organic compound represented by the above formula (1), it preferably contains at least one additional ligand selected from the ligands derived from the organic compound represented by the following formula (3), and the ligands derived from any of succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride. It is more preferred that the aforementioned additional ligands do not contain the cross-linking groups represented by the above general formulas (a-1) to (a-4).

[0238] R 3A COOH(3)

[0239] In the formula, R 3A It is a monovalent organic group having 1 to 20 carbon atoms.

[0240] When a compound containing such an additional ligand is used in a metal-containing film-forming composition, a cross-linking reaction during firing can be promoted, and the firing temperature at this time can be in a low temperature region. In addition, by promoting the cross-linking reaction, a dense metal-containing film can be formed, and etching resistance can be improved, which is ideal.

[0241] The ligand derived from the organic compound represented by formula (3) preferably contains at least one of an aromatic ring, a heteroaromatic ring, and an alicyclic structure, and examples thereof include the following.

[0242] [Chemistry 26]

[0243]

[0244] In the above formula, R 3AeIt is a monovalent organic group having 1 to 10 carbon atoms, n is 1 to 10, and * represents a bonding portion to the carbonyl carbon.

[0245] The ligand derived from any of succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride is preferably unsubstituted or substituted with a monovalent organic group having 1 to 10 carbon atoms, and is more preferably unsubstituted.

[0246] When a metal-containing film-forming composition containing a compound further containing an additional ligand derived from such an organic compound is used, dry etching resistance can be improved with minimum deterioration of the filling property, which is preferable.

[0247] When the aforementioned (A) metal-containing film-forming compound contains at least one additional ligand selected from a ligand derived from an organic compound represented by the above formula (3) and a ligand derived from any of succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, it is preferred that it contains a compound having any one of the structures shown below or a mixture of these compounds.

[0248] [Chemistry 27]

[0249]

[0250] The above R 3a is a monovalent organic group having 1 to 20 carbon atoms and not containing a crosslinking group represented by the above general formulae (a-1) to (a-4), or any of the following structures, R 1A Same as R in the above formula (A-1) 1A , R 2A Same as R in formula (1) 2A , n is 1 to 20, and M is the same as M in the above formula (A-1).

[0251] [Chemistry 28]

[0252]

[0253] In the above formula, R 3b It is an alkyl group having 1 to 10 carbon atoms, and * represents a bonding portion to the carbonyl carbon.

[0254] Furthermore, in addition to the ligand derived from the organic compound represented by the above formula (1) and the above-mentioned additional ligand, a ligand derived from a divalent or trivalent alcohol and / or a ligand derived from a β-diketone may be contained.

[0255] When such a compound is used in a metal-containing film-forming composition, a cross-linking reaction during firing can be promoted, and the firing temperature at this time can be in the low temperature domain. Therefore, a dense metal-containing film can be formed by promoting the cross-linking reaction, which can improve the etching resistance, and is therefore ideal.

[0256] The divalent or trivalent alcohols include, for example, the compounds described in paragraphs

[0055] to

[0060] of Japanese Patent No. 6189758, and any of the following compounds described in paragraph

[0061] is preferred.

[0257] [Chemistry 29]

[0258]

[0259] The β-diketone is preferably a structure represented by the following formula (3-a).

[0260] [Chemistry 30]

[0261]

[0262] In the above formula, R 3A and R 3B are each independently a monovalent organic group having 1 to 20 carbon atoms, R 3c It is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

[0263] The above R 3A and R 3B , each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group or a carbonyloxy hydrocarbon-substituted hydrocarbon group, more preferably an alkyl group, an aryl group, an alkoxy group or an alkoxycarbonylalkyl group, and still more preferably a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group or a methoxycarbonylmethyl group.

[0264] The above R 3c It is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom.

[0265] β-diketones, specifically, for example, 2,4-pentanedione, 3-methyl-2,4-pentanedione, 3-ethyl-2,4-pentanedione, acetoacetate, α-alkyl-substituted acetoacetate, β-ketovalerate, benzoyl acetate, 1,3-acetone dicarboxylate, malonic acid diester, di-tert-butyl malonate, α-alkyl-substituted malonic acid diester, α-cycloalkyl-substituted malonic acid diester, and α-aryl-substituted malonic acid diester, etc. More preferred are 2,4-pentanedione, 3-methyl-2,4-pentanedione, ethyl acetoacetate, diethyl malonate, or di-tert-butyl malonate, and 2,4-pentanedione, 3-methyl-2,4-pentanedione, or di-tert-butyl malonate are even more preferred.

[0266] When such a compound is used in a metal-containing film-forming composition, a crosslinking reaction can be promoted during firing, and the firing temperature can be low temperature. By promoting the crosslinking reaction, a dense metal-containing film can be formed, and etching resistance can be improved, which is ideal.

[0267] The above-mentioned (A) metal-containing film-forming compound may contain, in addition to the ligands derived from the organic compound represented by formula (1), one or more ligands of different structures selected from the ligands derived from the organic compound represented by formula (3) and the additional ligands derived from the ligands of any one of succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, and may be appropriately adjusted in accordance with the necessary properties required when used in the metal-containing film-forming composition. In addition, it may contain ligands derived from the above-mentioned divalent or trivalent alcohol and / or ligands derived from the above-mentioned β-diketone, and may be appropriately adjusted in accordance with the necessary properties required when used in the metal-containing film-forming composition.

[0268] When the metal-containing film-forming compound (A) contains a ligand different from the ligand derived from the organic compound represented by formula (1), it is preferred that the metal-containing film-forming compound (A) contains one or more ligands of different structures derived from succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, or cyclohexane dicarboxylic anhydride, and it is more preferred that the metal-containing film-forming compound (A) contains one or more ligands of different structures derived from succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, or cyclohexane dicarboxylic anhydride. By using the carbonyl ligand as the organic compound represented by formula (1), the storage stability of the metal-containing film-forming compound (A) can be improved.

[0269] In the above-mentioned (A) metal-containing film-forming compound, the content of the ligands derived from the organic compound represented by the above formula (1) is preferably 10 mol% or more of the total content of the ligands coordinated to the metal atom M, more preferably 30 mol% or more, and even more preferably 50 mol% or more, and the upper limit is preferably 100 mol%. The ligands other than the ligands derived from the organic compound represented by the above formula (1) are preferably 90 mol% or less of the total content of the ligands coordinated to the metal atom M, more preferably 70 mol% or less, and even more preferably 50 mol% or less, and the lower limit is preferably 0 mol%. It may also contain ligands other than the ligands described above, such as ligands derived from an alkyl group having 1 to 10 carbon atoms, and they are preferably 0 mol% to 50 mol% of the total content of the ligands coordinated to the metal atom M, and the content is more preferably 0 mol% to 30 mol%.

[0270] If the content of the ligand derived from the organic compound represented by the above formula (1) is 10 mol% or more, the embedding property of the metal-containing film-forming composition will be excellent, which is ideal. When the metal-containing film-forming composition is used in the process of embedding a finer pattern, it is preferred to increase the content of the ligand derived from the organic compound represented by the above formula (1), and a content of 50 mol% or more is particularly preferred.

[0271] <Synthesis of Metal-Containing Film-Forming Compound>

[0272] The metal-containing film-forming compound (A) of the present invention is, for example, a compound selected from one or more of a hydrolyzate of a metal compound represented by the aforementioned formula (A-1), a condensate of a metal compound represented by the aforementioned formula (A-1), and a hydrolysis-condensate of a metal compound represented by the aforementioned formula (A-1), and contains a ligand from an organic compound represented by the aforementioned formula (1). If it is a method for obtaining such a compound, there is no particular limitation on its synthesis method. For example, it can be obtained by reacting one or more of a hydrolyzate of a metal compound represented by the aforementioned formula (A-1), a condensate of a metal compound represented by the aforementioned formula (A-1), and a hydrolysis-condensate of a metal compound represented by the aforementioned formula (A-1) with an organic compound represented by the aforementioned formula (1).

[0273] Or (A) the metal-containing film-forming compound may be a metal-containing film-forming compound obtained by hydrolyzing or condensing, or hydrolyzing and condensing, a metal compound represented by the following general formula (A-2) having a ligand derived from an organic compound represented by formula (1).

[0274] (R 2A COXCOO x M(OR 1A ) y (A-2)

[0275] Wherein, M is Ti, Zr, or Hf, R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A It is a divalent organic group having 2 to 20 carbon atoms and containing at least one crosslinking group represented by the above general formulae (a-1) to (a-4), X is a divalent organic group having 2 to 20 carbon atoms, x+y=4, and x and y are integers greater than 1.

[0276] That is, the method for producing a metal-containing film-forming compound of the present invention comprises the following steps:

[0277] reacting an organic compound represented by the following formula (1) with one or more selected from the group consisting of a hydrolyzate of a metal compound represented by the following formula (A-1), a condensate of a metal compound represented by the following formula (A-1), and a hydrolysis-condensate of a metal compound represented by the following formula (A-1) or more thereof; or

[0278] The metal compound represented by the following general formula (A-2) is hydrolyzed or condensed, or hydrolyzed and condensed.

[0279] M(OR 1A )4 (A-1)

[0280] R 2A COXCOOH (1)

[0281] Wherein, M is Ti, Zr, or Hf, R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A It is a divalent organic group having 2 to 20 carbon atoms and containing at least one crosslinking group represented by any of the following general formulae (a-1) to (a-4), and X is a divalent organic group having 2 to 20 carbon atoms.

[0282] [Chemistry 31]

[0283]

[0284] In the above general formulas (a-1) to (a-4), R a is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding portion.

[0285] (R 2A COXCOO x M(OR 1A ) y (A-2)

[0286] Wherein, M is Ti, Zr, or Hf, R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A It is a divalent organic group having 2 to 20 carbon atoms and containing at least one crosslinking group represented by the above general formulae (a-1) to (a-4), X is a divalent organic group having 2 to 20 carbon atoms, x+y=4, and x and y are integers greater than 1.

[0287] If it is a compound selected from one or more of the hydrolyzate of the metal compound represented by the formula (A-1), the condensate of the metal compound represented by the formula (A-1), and the hydrolysis-condensation product of the metal compound represented by the formula (A-1), it has at least one [metal]-[oxygen]-[metal] bond, and when it is used to form a metal-containing film, it can provide a metal-containing film with high hardness and excellent density. In addition, by hydrolyzing or condensing, or hydrolyzing and condensing during the synthesis of the compound, the volume shrinkage accompanying the condensation reaction during the film firing can be reduced, thereby further improving the landfill characteristics.

[0288] The hydrolysis or hydrolysis condensation of the metal compound represented by formula (A-1) or the metal compound represented by formula (A-2) (hereinafter referred to as metal monomer) can be produced in the absence of a catalyst, acid or base catalyst. At this time, as for the acid catalyst, one or more compounds selected from inorganic acids, aliphatic sulfonic acids, aromatic sulfonic acids, aliphatic carboxylic acids and aromatic carboxylic acids can be used as acid catalysts to produce the target product. Specific acid catalysts include hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, maleic acid, fumaric acid, benzoic acid and the like. The amount of the catalyst used is preferably 1×10 -6 ~10 mol, more preferably 1×10 -5 ~5 mol, more preferably 1×10 -4 ~1 mol.

[0289] Alternatively, the monomer containing the metal M may be hydrolyzed and condensed in the presence of a base catalyst. Examples of the base catalyst used in this case include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, hexamethylenediamine, dimethylamine, diethylamine, ethylmethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, dicyclohexylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclocyclononene, diazabicycloundecene, hexamethylenetetramine, aniline, N,N-dimethylaniline, pyridine, N,N-dimethylethanolamine, N,N-di Ethylethanolamine, N-(β-aminoethyl)ethanolamine, N-methylethanolamine, N-methyldiethanolamine, N-ethylethanolamine, N-n-butylethanolamine, N-tert-butylethanolamine, N-tert-butyldiethanolamine, N,N-dimethylaminopyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, tetramethylammonium hydroxide, choline hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc. The amount of the catalyst used is preferably 1×10 mol relative to 1 mol of the monomer containing the metal M. -6 mol~10 mol, more preferably 1×10 -5 mol~5 mol, more preferably 1×10 -4 Mole~1 mole.

[0290] When the metal-containing compound is obtained from these metal-containing monomers by hydrolysis or hydrolysis condensation, the amount of water added is preferably 0.01 to 10 moles, more preferably 0.05 to 5 moles, even more preferably 0.1 to 3 moles, and particularly preferably 0.1 to 1 mole per mole of the hydrolyzable substituent bonded to the metal-containing monomer. If 10 moles or less is added, the equipment used for the reaction will not become too large and thus it is economical, and the stability of the metal-containing compound will not be impaired, so it is preferred.

[0291] As for the operation method, the monomer containing metal M is added to the aqueous catalyst solution to start the hydrolysis condensation reaction. At this time, an organic solvent may be added to the aqueous catalyst solution, or the monomer containing metal M may be diluted with an organic solvent in advance, or both may be performed. The reaction temperature is preferably 0 to 200°C, more preferably 5 to 150°C. When the monomer containing metal M is added dropwise, it is preferably kept at 5 to 150°C and then matured at 20 to 150°C.

[0292] In addition, as for other reaction operations, water or a water-containing organic solvent is added to the metal M-containing monomer or the organic solvent containing the metal M-containing monomer to start the hydrolysis reaction. At this time, the catalyst can be added to the metal M-containing monomer or the organic solvent containing the metal M-containing monomer, or it can be added to water or the water-containing organic solvent. The reaction temperature is preferably 0 to 200°C, more preferably 5 to 150°C. When the metal M-containing monomer is added dropwise, the temperature is maintained at 5 to 150°C, and then it is matured at 20 to 150°C.

[0293] The organic solvent that can be added to the aqueous catalyst solution or that can dilute the metal-containing compound is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, acetonitrile, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, 3-methoxy Preferably, the present invention comprises methyl propionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, γ-butyrolactone, acetylacetone, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, methyl pivaloyl acetate, methyl isobutyryl acetate, methyl caproyl acetate, methyl lauroyl acetate, 1,2-ethanediol, 1,2-propylene glycol, 1,2-butanediol, 1,2-pentanediol, 2,3-butanediol, 2,3-pentanediol, glycerol, diethylene glycol, hexylene glycol, and mixtures thereof.

[0294] The amount of the organic solvent used is preferably 0 to 1,000 ml, particularly preferably 0 to 500 ml, based on 1 mol of the metal-containing compound. If the amount of the organic solvent used is 1,000 ml or less, the reaction vessel will not become too large, which is economical.

[0295] Afterwards, if necessary, a neutralization reaction of the catalyst is carried out, and the alcohol generated by the hydrolysis condensation reaction is removed under reduced pressure to obtain an aqueous solution of the reaction mixture. At this time, the amount of the acid or base that can be used for neutralization is preferably 0.1 to 2 equivalents relative to the acid or base used for the catalyst, and any substance can be used as long as it can become neutral.

[0296] Then, it is preferred to remove the byproducts such as alcohol generated by the hydrolysis condensation reaction from the reaction mixture. The temperature at which the reaction mixture is heated at this time varies depending on the type of the organic solvent added and the alcohol generated by the reaction, and is preferably 0 to 200°C, more preferably 10 to 150°C, and even more preferably 15 to 150°C. In addition, the degree of decompression at this time varies depending on the type of the organic solvent and alcohol to be removed, the exhaust device, the condensing device, and the heating temperature, and is preferably below atmospheric pressure, more preferably below 80 kPa absolute pressure, and even more preferably below 50 kPa absolute pressure. It is difficult to accurately know the amount of alcohol removed at this time, but it is desired to remove about 80% by mass or more of the generated alcohol.

[0297] The final desired solvent is added to the metal-containing compound solution, such as butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, 1-butanol, 2-butanol, 2-methyl-1-propanol, 4-methyl-2-pentanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipentyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monotert-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, etc.

[0298] By using such a metal-containing compound, a metal-containing film-forming composition having no change in characteristics over a long period of time and excellent storage stability can be provided.

[0299] The (A) metal-containing film-forming compound of the present invention can be produced by adding the organic compound represented by formula (1) to the metal-containing compound obtained by the above-mentioned hydrolysis or hydrolysis-condensation or to a reaction mixture containing these compounds.

[0300] Similarly, when producing the (A) metal-containing film-forming compound containing a ligand other than the formula (1), it is produced by adding an organic compound derived from the ligand to the metal-containing compound obtained by the above hydrolysis or hydrolysis-condensation or to a reaction mixture containing these compounds.

[0301] <Metal-Containing Film-Forming Composition>

[0302] Furthermore, the present invention can provide a metal-containing film-forming composition characterized by containing the above-mentioned (A) metal-containing film-forming compound and (B) an organic solvent.

[0303] If it is such a metal-containing film-forming composition, since it contains a metal-containing film-forming compound that has both high thermal fluidity and thermal curing properties, it can provide a metal-containing film material that has excellent dry etching resistance compared to known organic lower layer film materials, and has high filling properties and / or high planarization properties.

[0304] The 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 below.

[0305] <(B) Organic Solvent>

[0306] The (B) organic solvent that can be used in the metal-containing film-forming composition of the present invention is not particularly limited, and it is preferred that the organic solvent (B) can and / or disperse the above-mentioned (A) metal-containing film-forming compound, and optionally contain the later-mentioned (C) cross-linking agent, (D) surfactant, (E) acid generator, (F) metal oxide nanoparticles having an average primary particle size of less than 100 nm, other additives, etc.

[0307] 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 is preferably used.

[0308] The amount of the organic solvent to be added is preferably in the range of 200 to 10,000 parts, more preferably 250 to 5,000 parts, based on 100 parts by mass of the (A) metal-containing film-forming compound.

[0309] <(B-1) High Boiling Point Solvent>

[0310] In the metal-containing 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 of less than 180°C and one or more organic solvents having a boiling point of 180°C or higher ((B-1) high boiling point solvent). That is, the (B) organic solvent may contain the (B-1) high boiling point solvent, and the (B-1) high boiling point solvent may be one or more organic solvents having a boiling point of 180 degrees (180°C) or higher.

[0311] (B-1) High boiling point solvents, without particular limitation, such as hydrocarbons, alcohols, ketones, esters, ethers, and chlorine-based solvents, are preferably solvents that can dissolve and / or disperse the components of the metal-containing film-forming composition of the present invention. Specific examples of (B-1) high boiling point solvents include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, n-nonyl acetate, monohexyl acetate, and 1,2-dimethyl-2,4-pentanediol. Ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol n-butyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol Dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol methyl n-propyl ether, dipropylene glycol methyl ether ethyl Acid esters, 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., which can be used alone or in combination.

[0312] (B-1) A high boiling point solvent, which can be appropriately selected from the above range in combination with the temperature at which the metal-containing film-forming composition of the present invention is heat-treated. The boiling point of the high boiling point solvent is preferably 180°C to 300°C, and 200°C to 300°C is more ideal. If it is such a boiling point, there is no risk of volatilization becoming too fast during baking (heat treatment), and sufficient thermal fluidity can be obtained during film formation, and it is believed that a resist underlayer film with excellent filling / planarization characteristics can be formed. In addition, if it is such a boiling point, there is no situation where it does not volatilize after baking and remains in the film, so there is no risk of adverse effects on the film properties such as etching resistance.

[0313] When the high boiling point solvent (B-1) 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 desirable because sufficient thermal fluidity can be imparted during baking, and no residue remains in the film and no degradation of the film properties such as etching resistance is caused.

[0314] When the metal-containing film-forming composition is a metal-containing film-forming composition that can be used as a resist underlayer film used in a multilayer resist method, it may contain one or more of the above-mentioned (A) metal-containing film-forming compound and (B) organic solvent, and may contain additives such as (C) a crosslinking agent, (D) a surfactant, (E) an acid generator, and (F) metal oxide nanoparticles having an average primary particle size of 100 nm or less. In another aspect, the metal-containing film-forming composition of the present invention may further contain one or more of (C) a crosslinking agent, (D) a surfactant, and (E) an acid generator.

[0315] The metal-containing film-forming composition of the present invention may further contain components different from the above components, for example, additives for imparting a filling property and / or a planarizing property.

[0316] Examples of components contained in the metal-containing film-forming composition of the present invention other than the above-mentioned (A) metal-containing film-forming compound and (B) organic solvent will be described below.

[0317] [(C) Cross-linking agent]

[0318] In addition, in the metal-containing film-forming composition of the present invention, in order to improve the hardening property of the metal-containing film-forming compound and to further suppress the cross-mixing with the layer formed on the metal-containing film, such as the upper film of the resist, it may also contain (C) a crosslinking agent. There is no particular limitation on the crosslinking agent, and various well-known crosslinking agents 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, epoxy-based crosslinking agents, and phenol-based crosslinking agents (such as hydroxymethyl or alkoxymethyl crosslinking agents of polynuclear phenols). The content of the aforementioned (C) crosslinking agent is preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the aforementioned (A) metal-containing film-forming compound.

[0319] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylated melamine, hexabutoxymethylated melamine, alkoxy and / or hydroxyl-substituted melamines thereof, and partially self-condensed products thereof.

[0320] Specific examples of the acrylate crosslinking agent include dipentatriol hexaacrylate.

[0321] Specific examples of the glycoluril-based crosslinking agent include tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, alkoxy and / or hydroxyl-substituted products thereof, and partial self-condensation products thereof.

[0322] Specific examples of the benzoguanamine-based crosslinking agent include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, alkoxy and / or hydroxyl-substituted products thereof, and partial self-condensation products thereof.

[0323] Specific examples of the urea crosslinking agent include dimethoxymethylated dimethoxyethylene urea, alkoxy and / or hydroxyl-substituted products thereof, and partial self-condensates thereof.

[0324] Specific examples of the β-hydroxyalkylamide crosslinking agent include N,N,N',N'-tetrakis(2-hydroxyethyl)adipamide.

[0325] Specific examples of the isocyanurate crosslinking agent include triglycidyl isocyanurate and triallyl isocyanurate.

[0326] Specific examples of the aziridine crosslinking agent include 4,4′-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate].

[0327] Oxazoline crosslinking agents include, for example, 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.

[0328] Specific examples of the epoxy crosslinking agent include diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, poly(glycidyl methacrylate), trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether.

[0329] The polynuclear phenol-based crosslinking agent is specifically, for example, a compound represented by the following general formula (XL-1).

[0330] [Chemistry 32]

[0331]

[0332] In the formula, Q is a single bond or a q1-valent hydrocarbon group having 1 to 20 carbon atoms. R3 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. q1 is an integer of 1 to 5.

[0333] Q is a single bond or a q1-valent hydrocarbon group having 1 to 20 carbon atoms. Q1 is an integer of 1 to 5, preferably 2 or 3. Specifically, Q is a group in which q1 hydrogen atoms are removed from methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, and eicosane. R3 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specifically, the alkyl group having 1 to 20 carbon atoms includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, ethylhexyl, decyl, and eicosyl. Preferably, R3 is a hydrogen atom or a methyl group.

[0334] Examples of compounds represented by the general formula (XL-1) include the following compounds. 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 preferred. R3 is the same as described above.

[0335] [Chemistry 33]

[0336]

[0337] [Chemistry 34]

[0338]

[0339] <(D) Surfactant>

[0340] In order to improve the coating properties of spin coating, a surfactant (D) may be added to the metal-containing film-forming composition of the present invention. The surfactant may be, for example, those described in

[0142] to

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

[0341] <(E) Acid Generator>

[0342] In order to further promote the curing reaction of the metal-containing film-forming compound (A) described above, an acid generator may be added to the metal-containing film-forming composition of the present invention. Acid generators may be those that generate acid by thermal decomposition or those that generate acid by light irradiation, and both may be added. Specifically, materials described in paragraphs

[0061] to

[0085] of Japanese Patent Application Publication No. 2007-199653 may be added, but are not limited thereto.

[0343] 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, more preferably 0.1 to 10 parts, based on 100 parts by mass of the (A) metal-containing film-forming compound.

[0344] <(F) Metal Oxide Nanoparticles>

[0345] In addition, in order to further improve the dry etching resistance, the metal-containing film-forming composition of the present invention may contain (F) metal oxide nanoparticles. Specifically, metal oxide nanoparticles selected from the group consisting of zirconium oxide nanoparticles, hafnium oxide nanoparticles, titanium oxide nanoparticles, tin oxide nanoparticles, and tungsten oxide nanoparticles are preferred.

[0346] By selecting the above metal oxide, a metal-containing film having further excellent dry etching resistance can be formed.

[0347] The aforementioned (F) metal oxide nanoparticles preferably have an average primary particle size of less than 100 nm, an average primary particle size of less than 50 nm more preferably, an average primary particle size of less than 30 nm more preferably, and less than 15 nm particularly preferably. The average primary particle size of the aforementioned metal oxide nanoparticles before being dispersed in an organic solvent can be obtained by directly measuring the size of the primary particles from an electron microscope photograph. Specifically, the minor axis diameter and major axis diameter of each primary particle are measured, and the average is defined as the particle size of the particle. Then, for more than 100 particles, the volume (mass) of each particle and the rectangular block of the desired particle size are approximated and obtained, and the volume average particle size is obtained and defined as the average particle size. In addition, electron microscopes, using a transmission type (TEM), a scanning type (SEM) or a scanning transmission type (STEM) can all obtain the same results.

[0348] Within such a particle size range, good dispersibility can be exhibited in the metal-containing film-forming composition, and the dry etching resistance of the metal-containing film can be improved without deteriorating the filling property and planarization property of the dense part of the fine pattern structure.

[0349] When the (F) metal oxide nanoparticles are added, the amount thereof is preferably 5 to 50 parts, more preferably 10 to 30 parts, based on 100 parts by mass of the (A) metal-containing film-forming compound.

[0350] <Liquid Additives and Thermally Decomposable Polymers>

[0351] In the metal-containing film-forming composition of the present invention, the additive for imparting the embedding / planarizing property is preferably a liquid additive having a polyethylene glycol or polypropylene glycol structure, or a thermally decomposable polymer having a weight loss rate of 40% by mass or more between 30° C. and 250° C. and a weight average molecular weight of 300 to 200,000. The thermally decomposable polymer preferably contains a repeating unit having an acetal structure represented by the following general formula (DP1) or (DP1a).

[0352] [Chemistry 35]

[0353]

[0354] In the formula, R6 is a hydrogen atom or an optionally substituted saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms. 1 It is a saturated or unsaturated divalent organic group having 2 to 30 carbon atoms.

[0355] [Chemistry 36]

[0356]

[0357] In the formula, R 6a 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.

[0358] When the liquid additive or the thermally decomposable polymer is added, the amount thereof is preferably 5 to 100 parts, more preferably 10 to 50 parts, based on 100 parts by mass of the (A) metal-containing compound for forming a film.

[0359] <Flowability Promoter (BP)>

[0360] Furthermore, the metal-containing film-forming composition of the present invention may contain a fluidity enhancer (BP) as an additive for imparting a fill property and / or a planarizing property. The fluidity enhancer (BP) preferably has an organic group represented by the following general formula (bp1a) and an aromatic ring.

[0361] [Chemistry 37]

[0362]

[0363] In the formula, * represents the bonding site to the oxygen atom, R B is a divalent organic group having 1 to 10 carbon atoms, R A It is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.

[0364] The aforementioned fluidity promoter (BP) can impart thermal fluidity and thermal curing properties to the aforementioned metal-containing film-forming compound (A) by having an organic group represented by the aforementioned general formula (bp1a). In addition, the aforementioned fluidity promoter (BP) can alleviate the deterioration of the dry etching resistance of the metal-containing film-forming compound (A) by having an aromatic ring.

[0365] The fluidity improving agent (BP) preferably has at least one structural unit represented by any of the following general formulae (BP-1), (BP-2), (BP-3), (BP-4) and (BP-5).

[0366] (Constituent units: BP-1, BP-2 and BP-3)

[0367] [Chemistry 38]

[0368]

[0369] In the above general formulae (BP-1) and (BP-2), W1 and W2 are each independently a benzene ring or a naphthalene ring, and the hydrogen atoms in the benzene ring and the naphthalene ring may be substituted by a hydrocarbon group having 1 to 6 carbon atoms. a1 It is the following general formula (4). Y is a group represented by the following general formula (5). n1 is 0 or 1, n2 is 1 or 2, and V each independently represents a hydrogen atom or a linking part.

[0370] [Chemistry 39]

[0371]

[0372] In the above general formula (BP-3), Z1 is a group represented by the following general formula (6), R a1 It is the following general formula (4): n4 is 0 or 1, n5 is 1 or 2, and V each independently represents a hydrogen atom or a linking part.

[0373] [Chemistry 40]

[0374]

[0375] * indicates a bonding portion with an oxygen atom.

[0376] [Chemistry 41]

[0377]

[0378] * indicates an atomic bond.

[0379] [Chemistry 42]

[0380]

[0381] In the above general formula (6), W1, W2, Y and n1 are the same as described above.

[0382] If it is a resin having a structural unit represented by any of the above general formulas (BP-1), (BP-2) and (BP-3), it has excellent heat resistance because a condensed carbon ring with a high carbon density containing a cardo structure is introduced. Due to the above characteristics, even if a high-temperature baking treatment is performed, a metal-containing film that fills a high-height substrate without generating pores can be formed. In addition, the dry etching resistance is also excellent, so even if it is added to the metal-containing film-forming composition of the present invention, heat resistance and thermal fluidity can be imparted without significantly deteriorating the excellent dry etching resistance of the metal-containing film-forming composition.

[0383] The resin having a structural unit represented by any of the above general formulae (BP-1), (BP-2) and (BP-3) may be a compound represented by the following general formulae (bp-1) and / or (bp-2) and / or (bp-3).

[0384] [Chemistry 43]

[0385]

[0386] In the above general formulas (bp-1) and (bp-2), W1, W2, R a1 , Y, n1, and n2 are the same as those described for the above general formulas (BP-1) and (BP-2).

[0387] [Chemistry 44]

[0388]

[0389] In the above general formula (bp-3), Z1, R a1 , n4, and n5 are the same as described for the above general formula (BP-3).

[0390] Specific examples of the resin having a structural unit represented by any of the general formulae (bp-1), (bp-2) and (bp-3) include the following compounds, but are not limited to these.

[0391] [Chemistry 45]

[0392]

[0393] For the above-mentioned resins (bp-1), (bp-2) and (bp-3), the ratio Mw / Mn (i.e., the degree of dispersion) of the polystyrene-converted weight average molecular weight Mw to the number average molecular weight Mn measured by gel permeation chromatography is preferably in the range of 1.00≤Mw / Mn≤1.25, and even better is 1.00≤Mw / Mn≤1.10.

[0394] If the compound has a dispersion degree within such a range, the thermal fluidity of the metal-containing film-forming composition will be improved, and when it is blended with a material, a metal-containing film-forming composition having better filling properties and / or planarization properties can be provided.

[0395] Or a resin having a structural unit represented by any of the above-mentioned general formulas (BP-1), (BP-2) and (BP-3) may be a polymer having a repeating unit represented by the following general formulas (bp-4) and / or (bp-5) and / or (bp6).

[0396] [Chemistry 46]

[0397]

[0398] In the above general formulas (bp-4) and (bp-5), W1, W2, R a1 , Y, n1, and n2 are the same as those described for the above general formulae (BP-1) and (BP-2), and L1 is a divalent organic group having 1 to 40 carbon atoms.

[0399] [Chemistry 47]

[0400]

[0401] In the above general formula (bp-6), Z1, R a1 , n4, and n5 are the same as those described for the aforementioned general formula (BP-3), and L1 is a divalent organic group having 1 to 40 carbon atoms.

[0402] These are polymers obtained by using compounds represented by any of the above general formulae (bp-1), (bp-2) and (bp-3), and due to the use of the above compounds, they have excellent dry etching resistance and heat resistance. In addition, since they are polymers having repeating units rather than monomers, they have less dissipated gas components, and since they are polymers having a molecular weight distribution, their crystallinity is moderated, and it is also expected that the film-forming properties will be improved.

[0403] The linking group L1 constituting any repeating unit of the general formulae (bp-4), (bp-5) and (bp-6) is a divalent organic group having 1 to 40 carbon atoms, and specific examples thereof include the following.

[0404] [Chemistry 48]

[0405]

[0406] Furthermore, the linking group L1 of the aforementioned polymer is preferably the following general formula (10).

[0407] [Chemistry 49]

[0408]

[0409] In the above general formula (10), R1 is a hydrogen atom or an aromatic ring-containing organic group having 6 to 20 carbon atoms, and the chain represents an atomic bond.

[0410] The above general formula (10) can be specifically listed as follows. Among the following, considering the availability of raw materials, methylene, that is, R1 is preferably a hydrogen atom.

[0411] [Chemistry 50]

[0412]

[0413] The polymer having a repeating structural unit represented by any of the general formulae (bp-4), (bp-5) and (bp-6) preferably has a polystyrene-equivalent weight average molecular weight of 1,000 to 12,000 as determined by gel permeation chromatography, and preferably has a Mw of 2,000 to 10,000.

[0414] If the molecular weight is within such a range, the solubility in organic solvents can be ensured, and the sublimation generated during baking can be suppressed. In addition, the thermal fluidity of the metal-containing film-forming composition becomes good, so when mixed with a material, a metal-containing film-forming composition with better filling and / or planarization properties can be provided.

[0415] (Constituent unit: BP-4)

[0416] [Chemistry 51]

[0417]

[0418] In the formula, m3 and m4 represent 1 or 2, and Z2 represents a single bond or any of the structures represented by the following general formula (7). x It is any of the structures represented by the following general formula (8).

[0419] [Chemistry 52]

[0420]

[0421] In the formula, * represents an atomic bond, l represents an integer from 0 to 3, and R az ~R fz Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with fluorine, a phenyl group, or a phenylethyl group, and R az With R bz They can also form cyclic compounds.

[0422] [Chemistry 53]

[0423]

[0424] In the formula, * represents a bonding site to an aromatic ring, and Q1 is a linear saturated hydrocarbon group having 1 to 30 carbon atoms, or a structure represented by the following general formula (9).

[0425] [Chemistry 54]

[0426]

[0427] In the formula, * represents the bonding site to the carbonyl group, R i It is the above general formula (4). j It represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. 3z and n 4z represents the number of substituents on the aromatic ring, and each represents an integer from 0 to 7. 3z +n 4z It is between 0 and 7. 5z Represents 0 to 2.

[0428] In view of dry etching resistance and heat resistance, in the above general formula (BP-4), Z2 is preferably a single bond or any of the structures represented by the above formula (7).

[0429] [Chemistry 55]

[0430]

[0431] In the formula, * represents an atomic bond, and l is the same as the above formula (7).

[0432] In the above general formula (8), when Q1 represents a linear hydrocarbon group having 1 to 30 carbon atoms, the methylene group constituting Q1 may be substituted with an oxygen atom or a carbonyl group. From the viewpoint of dry etching resistance and heat resistance, Q1 is preferably a structure represented by the above general formula (9).

[0433] The compounds containing the constituent units represented by the above general formula (BP-4) have a structure in which the aromatic rings are connected by a single bond or the general formula (7), so the carbon density is high, and the metal-containing film-forming composition constituting these compounds has excellent heat resistance. In addition, the linking group Z2, as shown in the above formula (7), can be selected from a variety of linking groups to match the desired performance. In particular, with respect to the linking group Z2, by introducing the structure represented by the above formula (7), it is possible to impart heat resistance and / or etching resistance without damaging the film-forming property. In addition, due to the highly flexible terminal portion R x Even if it contains a rigid aromatic ring structure, the metal-containing film-forming composition can be formed into a thick film without defects such as cracks. xContaining the terminal group Q1 that imparts thermal fluidity, the terminal group Q1 can be introduced in any proportion to match the required performance with a soft hydrocarbon structure that helps improve thermal fluidity and a rigid aromatic ring structure that helps etching resistance and heat resistance. As described above, the metal-containing film-forming composition to which these compounds are added can achieve both embedding and / or planarization properties and heat resistance in a high-dimensional manner, and can form a thick film in accordance with the required properties.

[0434] (Constituent unit: BP-5)

[0435] [Chemistry 56]

[0436]

[0437] In the above general formula (BP-5), R 1 is a saturated monovalent organic group having 1 to 30 carbon atoms or an unsaturated monovalent organic group having 2 to 30 carbon atoms, X1 is a divalent organic group having 1 to 30 carbon atoms, R a1 It is the above-mentioned general formula (4). p is an integer of 0 to 5, q1 is an integer of 1 to 6, p+q1 is an integer of 1 to 6, and q2 is 0 or 1.

[0438] In the above general formula (BP-5), X1 represents a divalent organic group having 1 to 30 carbon atoms, for example, a methylene group, an alkanediyl group such as an ethanediyl group, a propanediyl group, a butanediyl group, a pentanediyl group, a hexanediyl group, an octanediyl group, a decanediyl group, a cyclopropanediyl group, a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group, a cyclooctanediyl group, a cyclodecanediyl group, a methylcyclohexanediyl group, an ethylcyclohexanediyl group, a bicyclo[2.2.1]heptanediyl group, a bicyclo[2.2.2]octanediyl group, a tricyclo[5.2.1.0] 2,6 ]Decanediyl (dicyclopentylidene), tricyclo[3.3.1.1 3,7 ]Decanediyl, tetracyclo[6.2.1.1 3,6 .0 2,7 ] polycyclic cycloalkanediyl such as dodecanediyl and adamantanediyl, and arenediyl such as phenylene and naphthylene.

[0439] Examples of the alkanediyloxy group represented by X1 include groups formed by combining the above alkanediyl group with an oxygen atom, etc. Examples of the cycloalkanediyloxy group represented by X1 include groups formed by combining the above cycloalkanediyl group with an oxygen atom, etc.

[0440] A part or all of the hydrogen atoms possessed by the above-mentioned alkanediyl, cycloalkanediyl, alkanediyloxy, cycloalkanediyloxy and arenediyl groups may be substituted. The substituents may be, for example, a Examples of substituents which the organic groups represented may have include the same groups and the like.

[0441] The organic group represented by X1 is, for example, a group represented by the following formula.

[0442] [Chemistry 57]

[0443]

[0444] In the above formula, * represents an atomic bond.

[0445] As for the above-mentioned X1, from the viewpoint of raw material availability, for example, a methylene group is preferred.

[0446] Specific examples of the resin having the structural unit represented by the general formula (BP-5) include the following.

[0447] [Chemistry 58]

[0448]

[0449] [Chemistry 59]

[0450]

[0451] The polymer containing the structural unit represented by the general formula (BP-5) has a structure in which the aromatic ring is connected by an organic group (X1), so the carbon density is high, and the metal-containing film-forming composition containing these compounds exhibits high dry etching resistance and excellent heat resistance. Furthermore, the organic group of the structure represented by the general formula (4) above, which helps to improve thermal fluidity, is directly bonded to the aromatic ring of the parent core structure of the resin via an oxygen atom, so the metal-containing film-forming composition to which these polymers are added can take into account both the filling and / or flattening properties and the heat resistance and / or etching resistance in a high dimension. In addition, the aromatic ring structure of the parent core is not too rigid, but forms a repeating structure in which the organic group (X1) of the connecting group is separated, so that the metal-containing film-forming composition can be formed without defects such as cracks.

[0452] In the metal-containing film-forming composition of the present invention, the content of the fluidity promoter (BP) is preferably 50 mass % or less, more preferably 30 mass % or less, and even more preferably 20 mass % or less based on 100 mass parts of the metal-containing film-forming compound.

[0453] The amount of the fluidity enhancer added can be adjusted to any ratio in accordance with the required characteristics of the process using the metal-containing film-forming composition of the present invention. When it is desired to minimize the degradation of the dry etching resistance, the ratio of the fluidity enhancer is reduced, and when it is desired to further improve the embedding property / planarization property while allowing a certain degree of degradation of the dry etching resistance, the ratio of the fluidity enhancer is increased.

[0454] <Method for Forming Metal-Containing Film>

[0455] The present invention provides a method for forming a metal-containing film (filling film) that functions as, for example, 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.

[0456] 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 spin coating or the like. By using the spin coating method or the like, good filling characteristics can be obtained. After spin coating, the solvent is evaporated and mixed with the resist upper film and the resist intermediate film is prevented, and baking (heat treatment) is performed to promote the cross-linking reaction. The baking is preferably performed in the range of 100°C to 600°C for 10 to 600 seconds, and more preferably in the range of 200°C to 500°C for 10 to 300 seconds. Considering the damage to the device and the influence on the deformation of the wafer, the upper limit of the heating temperature of the wafer processing for lithography is preferably set to be below 600°C, and more preferably below 500°C.

[0457] Furthermore, the method for forming an anti-etching underlayer film using the metal-containing film-forming composition of the present invention can also be carried out by coating the metal-containing film-forming composition of the present invention on a processed substrate by a spin coating method or the like in the same manner as described above, and firing the above-mentioned metal-containing film-forming composition 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.

[0458] The metal-containing film of the present invention is formed by firing in such an oxygen environment to obtain a fully hardened film. It is also possible that the gas environment during baking is in the air. In order to reduce oxygen, it is ideal to prevent oxidation of the metal-containing film by pre-sealing in inert gases such as N2, Ar, and He. In order to prevent oxidation, the oxygen concentration must be controlled, preferably below 1000ppm, more preferably below 100ppm (volume basis). If the metal-containing film is prevented from being oxidized during baking, there is no absorption increase or etching resistance reduction, so it is ideal.

[0459] <Pattern Formation Method Using a Metal Film-Forming Composition>

[0460] The present invention also provides a pattern forming method, which is a pattern forming method using the above-mentioned metal-containing film-forming composition and utilizing a two-layer resist process, and is a method for forming a pattern on a processed substrate, characterized by comprising the following steps:

[0461] (I-1) After applying the metal-containing film-forming composition on a substrate to be processed, a metal-containing film is formed by heat treatment,

[0462] (I-2) forming a resist upper layer film on the aforementioned metal-containing film using a photoresist material,

[0463] (I-3) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0464] (I-4) using the patterned resist upper layer film as a mask to dry-etch the metal-containing film to transfer the pattern, and

[0465] (I-5) The substrate to be processed is processed using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0466] Since the resist upper layer film in the above-mentioned two-layer resist treatment shows resistance to etching by chlorine-based gas, in the above-mentioned two-layer resist treatment, dry etching of the metal-containing film using the resist upper layer film as a mask is preferably performed using an etching gas containing chlorine-based gas as the main component.

[0467] The present invention also provides a pattern forming method, which is a pattern forming method using the above-mentioned metal-containing film-forming composition and utilizing a three-layer resist process, and is a method for forming a pattern on a processed substrate, characterized by comprising the following steps:

[0468] (II-1) After applying the metal-containing film-forming composition on a substrate to be processed, a metal-containing film is formed by heat treatment,

[0469] (II-2) forming a resist intermediate film on the aforementioned metal-containing film,

[0470] (II-3) forming a resist upper layer film on the resist intermediate film using a photoresist material,

[0471] (II-4) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0472] (II-5) using the patterned resist upper layer film as a mask, dry etching is performed to transfer the pattern to the resist intermediate layer film,

[0473] (II-6) using the resist intermediate film having the transferred pattern as a mask, dry etching the transferred pattern on the metal-containing film, and

[0474] (II-7) The substrate to be processed is processed using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0475] Here, use Figure 1The present invention provides a method for forming a pattern by a three-layer resist process using the metal-containing film-forming composition. Figure 1 (A), on the processed layer 2 of the processed substrate 1A in which the processed layer 2 is formed on the substrate 1, a metal-containing film 3 is formed using the above-mentioned metal-containing film-forming composition, a resist intermediate film 4 is formed on the above-mentioned metal-containing film 3 using a resist intermediate film material, and a resist upper film 5 is formed on the above-mentioned intermediate film 4 using a photoresist material. Then, as Figure 1 (B), the exposed portion of the resist upper film is exposed in a 6-step pattern. Then, as Figure 1 (C), developing with a developer is performed to form a resist upper film pattern 5a on the resist upper film. Figure 1 (D), the patterned resist upper film is used as a mask to dry-etch the resist intermediate film transfer pattern to form a resist intermediate film pattern 4a. Then, as Figure 1 (E), using the resist intermediate film with the transferred pattern as a mask, dry etching is performed on the metal-containing film transfer pattern to form a metal-containing film pattern 3a. Then, Figure 1 (F) The patterned metal-containing film is used as a mask to process the processing layer 2 of the processing substrate 1A, thereby forming a pattern 2a on the processing substrate 1A.

[0476] The silicon-containing resist intermediate film that can be used as an example of the intermediate film in the above three-layer resist process shows resistance to etching by chlorine-based gas. Therefore, in the above three-layer resist process, when the silicon-containing resist intermediate film is used as the intermediate film, the dry etching of the metal-containing film using the silicon-containing resist intermediate film as a mask is preferably performed using an etching gas mainly composed of chlorine-based gas.

[0477] The above three layers of resist are treated with silicon-containing resist intermediate films. It is also ideal to use a polysiloxane-based intermediate film. By giving the silicon-containing resist intermediate film an anti-reflection effect, reflection can be suppressed. Especially for 193nm exposure, if a material containing many aromatic groups and having a high etching selectivity with the substrate is used for the organic film, the k value is high and the substrate reflection is high, but by giving the silicon-containing resist intermediate film an absorption with an appropriate k value, reflection can be suppressed and the substrate reflection can be reduced to less than 0.5%. For the silicon-containing resist intermediate film with an anti-reflection effect, it is ideal to use anthracene for 248nm and 157nm exposure, and to use a polysiloxane with a pendant phenyl group or a silicon-silicon bonded light-absorbing group for 193nm exposure and cross-linked with acid or heat.

[0478] In addition, the present invention provides a pattern forming method as another aspect of the pattern forming method using a four-layer resist process using such a resist underlayer film forming composition, which is characterized by having the following steps: forming a metal-containing film on a processed substrate using the above-mentioned metal-containing film forming composition, forming a silicon-containing resist intermediate film on the metal-containing film using a silicon-containing resist intermediate film material, forming an organic anti-reflective film (BARC) or a sealing film on the silicon-containing resist intermediate film, and applying light to the BARC or the sealing film. The resist material forms a resist upper film, the resist upper film is pattern-exposed, and then developed with a developer to form a pattern on the resist upper film, the patterned resist upper film is used as a mask to transfer the pattern to the BARC or the sealing film and the silicon-containing resist intermediate film by dry etching, the silicon-containing resist intermediate film with the transferred pattern is used as a mask to transfer the pattern to the metal-containing film by dry etching, and the patterned metal-containing film is used as a mask to process the processed substrate to form a pattern on the processed substrate.

[0479] Furthermore, an inorganic hard mask may be formed instead of forming an intermediate film containing silicon. In this case, a pattern forming method is provided, which can form a pattern on a processed substrate, such as a semiconductor device circuit pattern. The method is characterized by having the following steps:

[0480] (III-1) After applying the metal-containing film-forming composition on a substrate to be processed, a metal-containing film is formed by heat treatment,

[0481] (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 aforementioned metal-containing film,

[0482] (III-3) forming an organic thin film on the aforementioned inorganic hard mask intermediate film,

[0483] (III-4) forming a resist upper layer film on the aforementioned organic thin film using a photoresist material,

[0484] (III-5) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0485] (III-6) using the patterned resist upper layer film as a mask, dry etching is performed to transfer the pattern to the organic thin film and the inorganic hard mask intermediate film,

[0486] (III-7) using the inorganic hard mask intermediate film having the transferred pattern as a mask, dry etching the transferred pattern on the metal-containing film, and

[0487] (III-8) The substrate to be processed is processed using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0488] 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 using a CVD method, an ALD method, or the like. For example, a method for forming a silicon nitride film is described in Japanese Patent 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. In addition, as an inorganic hard mask, it is best to use a SiON film that has a high effect as an anti-reflective film. The substrate temperature when forming the SiON film is 300 to 500°C, and the resist lower layer film needs to withstand a temperature of 300 to 500°C, so the metal-containing film needs to withstand a temperature of 300 to 500°C. The metal-containing film-forming composition used in the present invention has high heat resistance and can withstand high temperatures of 300° C. to 500° C., so it can be a combination of an inorganic hard mask formed by CVD or ALD and a metal-containing film formed by spin coating.

[0489] As described above, a photoresist film can be formed on the inorganic hard mask as a resist upper layer film, and an organic antireflection film (BARC) or a bonding film can be formed on the inorganic hard mask by spin coating and a photoresist film can be formed thereon. In particular, when a SiON film is used as an inorganic hard mask intermediate film, 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 benefit of forming a BARC is that it has the effect of reducing the tailing of the photoresist pattern directly on the SiON film.

[0490] For example, one aspect of the pattern forming method of the present invention is a pattern forming method, which is a method for forming a pattern on a processed substrate, characterized by having the following steps:

[0491] (IV-1) After applying the metal-containing film-forming composition on a substrate to be processed, a metal-containing film is formed by heat treatment.

[0492] (IV-2) forming an organic intermediate film on the aforementioned metal-containing film,

[0493] (IV-3) forming a combination of an inorganic hard mask interlayer film selected from a resist interlayer film containing silicon or a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film and an organic thin film on the aforementioned organic interlayer film,

[0494] (IV-4) forming a resist upper layer film using a photoresist material on the aforementioned silicon-containing resist intermediate film or the aforementioned organic thin film,

[0495] (IV-5) after pattern-exposing the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0496] (IV-6) using the patterned resist upper layer film as a mask, dry etching is performed to transfer the pattern to the silicon-containing resist intermediate film or the organic thin film and the inorganic hard mask intermediate film,

[0497] (IV-7) using the silicon-containing resist intermediate film or inorganic hard mask intermediate film to which the pattern has been transferred as a mask, and dry etching the pattern transferred on the organic intermediate film,

[0498] (IV-8) using the organic intermediate film having the transferred pattern as a mask to dry-etch the transferred pattern on the metal-containing film, and

[0499] (IV-9) The substrate to be processed is processed using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0500] In the above pattern forming method, the resist upper layer film may be positive or negative, and the same photoresist composition as commonly used may be used. In addition, the photoresist composition may also contain metal atoms such as Sn, In, Ga, Ge, Al, Ce, La, Cs, Zr, Hf, Ti, Bi, Sb, and Zn. When the resist upper layer film is formed using the above photoresist composition, it may be formed by a spin coating method, a CVD method, or an ALD method by vapor deposition.

[0501] When the photoresist composition is formed by spin coating, the resist is pre-baked after coating, preferably at 60 to 180°C for 10 to 300 seconds. Then, exposure is performed according to the usual method, and post-exposure baking (PEB) and development are performed to obtain a resist pattern. In addition, the thickness of the resist upper layer is not particularly limited, but 10 to 500 nm, particularly 20 to 400 nm, is preferred.

[0502] When the photoresist composition is formed by evaporation treatment using a CVD method or an ALD method, the resist composition is a metal oxide film with EUV sensitivity, and the metal is selected from Sn, Zr, Hf, Ti, Bi, Sb, etc., among which Sn with excellent EUV sensitivity is preferred. The film containing the metal oxide can be a photosensitive organic metal oxide film such as an organic tin oxide (for example, a halogenated alkyl Sn, an alkoxyalkyl Sn, or an amide alkyl Sn). Some specific examples of suitable precursors include trimethyltin chloride, dimethyltin dichloride, methyltin trichloride, tris(dimethylamino)methyltin(IV), and (dimethylamino)trimethyltin(IV).

[0503] The film containing metal oxide can be deposited by PECVD or PEALD using a Lam Vector (registered trademark) tool, for example. In the ALD embodiment, the Sn oxide precursor can be separated from the O precursor / plasma. The evaporation temperature is preferably in the range of 50°C to 600°C. The evaporation pressure is preferably between 100 and 6,000 mTorr. The flow rate of the precursor liquid of the film containing metal oxide (for example, organic tin oxide precursor) can be 0.01 to 10 cmm, and the gas flow rate (CO2, CO, Ar, N2) can be 100 to 10,000 sccm. The plasma power can use high-frequency plasma (for example, 13.56 MHz, 27.1 MHz, or higher frequency), which is 200 to 1,000 W per 300 mm wafer station. The evaporation thickness is preferably 100 to 2,000 angstroms.

[0504] The exposure light is high-energy radiation having a wavelength of 300 nm or less, and specifically, for example, excimer lasers of 248 nm, 193 nm, and 157 nm, soft X-rays of 3 to 20 nm, electron beams, X-rays, and the like.

[0505] The patterning method of the resist upper layer film is preferably optical lithography with a wavelength of 5 nm to 300 nm, direct writing using an electron beam, nanoimprinting, or a combination thereof.

[0506] Furthermore, the development method of the above-mentioned pattern forming method may be preferably alkali development or organic solvent development.

[0507] The obtained resist pattern is then used as a mask for etching. The etching of the silicon-containing resist intermediate film and the inorganic hard mask of the three-layer resist process is performed using a fluorine-based gas with the upper resist pattern as a mask. In this way, a silicon-containing resist intermediate film pattern and an inorganic hard mask pattern can be formed.

[0508] Next, the obtained silicon-containing resist intermediate film pattern and inorganic hard mask pattern are used as masks to perform etching of the metal-containing film. The etching of the metal-containing film is preferably performed using an etching gas mainly containing chlorine.

[0509] The etching of the processed object can be carried out according to the usual method. For example, if the processed object is SiO2, SiN, or a silicon dioxide-based low dielectric constant insulating film, etching can be carried out mainly using a fluorine-based gas. When the substrate is processed using fluorine-based gas etching, the silicon-containing resist intermediate film pattern of the three-layer resist treatment will be peeled off while the substrate is being processed.

[0510] The metal-containing film obtained from the metal-containing film-forming composition of the present invention has a characteristic of being excellent in etching resistance when etching the workpiece.

[0511] Furthermore, the object to be processed (substrate to be processed) is not particularly limited, and substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc., and substrates on which a layer to be processed is formed, etc. can be used. The processed layer can be 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, and can generally be formed to a thickness of 50 to 10,000 nm, particularly 100 to 5,000 nm. Furthermore, when forming the layer to be processed, the substrate and the layer to be processed can be made of different materials.

[0512] The pattern forming method using the metal-containing film-forming composition of the present invention preferably uses 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 and / or flattening properties, so even if the processed substrate has a structure or height difference (concave and convex) of more than 30nm in height, a flat hardened film can still be formed. The height of the structure or height difference of the above-mentioned processed substrate is preferably more than 30nm, more preferably more than 50nm, and more preferably more than 100nm. In the method of processing a substrate with a height difference of a pattern having the above-mentioned height, by forming a film with the metal-containing film-forming composition of the present invention and filling and / or flattening, the film thickness of the resist intermediate film and the resist upper film formed later can be made uniform, so the exposure depth tolerance (DOF) during optical lithography is easy to ensure, which is very ideal.

[0513] The present invention also provides a pattern forming method, as a pattern forming method using the above-mentioned metal-containing film-forming composition and utilizing a four-layer resist process, characterized in that it comprises the following steps: forming a metal-containing film on a substrate to be processed using the above-mentioned metal-containing film-forming composition, forming an organic intermediate film on the metal-containing film using an organic intermediate film material, forming a silicon-containing resist intermediate film on the organic intermediate film using a silicon-containing resist intermediate film material, forming an organic antireflective film (BARC) or a bonding film on the silicon-containing resist intermediate film as required, forming a silicon-containing resist intermediate film on the silicon-containing film or the BARC or bonding film using a silicon-containing resist intermediate film material; The photoresist material forms a resist upper film, and after the resist upper film is pattern-exposed, it is developed with a developer to form a pattern on the resist upper film, and the patterned resist upper film is used as a mask to transfer the pattern to the BARC or the sealing film and the silicon-containing resist intermediate film by dry etching, and the silicon-containing resist intermediate film with the transferred pattern is used as a mask to transfer the pattern to the organic intermediate film by dry etching, and the organic intermediate film is used as a mask to transfer the pattern to the metal-containing film, and the metal-containing film with the pattern formed is used as a mask to process the processed substrate to form a pattern on the processed substrate.

[0514] As the organic interlayer material that can be used for the organic interlayer, the 4,4'-(9-fluorenylene)bisphenol novolac resin (molecular weight 11,000) described in Japanese Patent Application Laid-Open No. 2005-128509, which is known as an underlayer film for a three-layer resist method or a two-layer resist method using a silicon resist composition, can be used. In addition, a plurality of resins including novolac resin that are known as resist underlayer materials for a two-layer resist method or a three-layer resist method can be used. Furthermore, when it is desired to improve heat resistance more than that of a conventional novolac, a polycyclic skeleton such as a 6,6'-(9-fluorenylene)-di(2-naphthol) novolac resin can be added, and a polyimide resin can be selected (for example, Japanese Patent Application Laid-Open No. 2004-153125).

[0515] The organic intermediate film can be formed on the substrate by spin coating using a composition solution, similar to the photoresist composition. After the organic lower film is formed by spin coating, it is preferably baked to evaporate the organic solvent. It is more ideal to use a baking temperature in the range of 80 to 400°C and a baking time in the range of 10 to 300 seconds.

[0516] Instead of using the above-mentioned organic resist underlayer film material, an organic hard mask formed by a CVD method or an ALD method may be used.

[0517] The organic interlayer film in the multilayer resist treatment is resistant to etching with a chlorine-based gas. In the multilayer resist treatment, dry etching of the metal-containing film using the organic interlayer film as a mask is preferably performed using an etching gas mainly containing a chlorine-based gas.

[0518] <Tone-reversal pattern forming method using a metal-containing film-forming composition>

[0519] Furthermore, the present invention provides a tone-reversal pattern forming method, which is a tone-reversal pattern forming method using the above-mentioned metal-containing film-forming composition, and is a method for forming a pattern on a processed substrate, characterized by having the following steps:

[0520] (V-1) forming a resist underlayer film on a substrate to be processed,

[0521] (V-2) forming a resist intermediate film, or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film and an organic thin film on the resist underlayer film,

[0522] (V-3) forming a resist upper layer film using a photoresist material on the aforementioned resist intermediate film or the combination of the inorganic hard mask intermediate film and the organic thin film,

[0523] (V-4) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0524] (V-5) using the patterned resist upper layer film as a mask, dry etching to transfer a pattern to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film,

[0525] (V-6) using the resist intermediate film or inorganic hard mask intermediate film to which the pattern has been transferred as a mask, dry etching is performed to transfer the pattern on the resist lower layer film,

[0526] (V-7) coating the metal-containing film-forming composition 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.

[0527] (V-8) etching back the metal-containing film on the resist underlayer film having the pattern formed thereon by chemical stripping agent or dry etching to expose the top surface of the resist underlayer film having the pattern formed thereon,

[0528] (V-9) the resist intermediate film or the hard mask intermediate film remaining on the top surface of the resist lower layer film is removed by dry etching,

[0529] (V-10) removing the aforementioned patterned resist underlayer film exposed on the surface by dry etching to form a reverse pattern of the original pattern on the metal-containing film,

[0530] (V-11) The metal-containing film having the reverse pattern formed therein is used as a mask to process the substrate to be processed, thereby forming a reverse pattern on the substrate to be processed.

[0531] use Figure 2 The present invention is directed to a method for forming a tonality-reversed pattern using a metal-containing film-forming composition. Figure 2 (G), on the processed layer 2 of the processed substrate 1A on which the processed layer 2 is formed on the substrate 1, a resist lower layer film 7 is formed, and on the resist lower layer film 7, a resist intermediate film 4, 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 is formed, and on the resist intermediate film 4, or the combination of an inorganic hard mask intermediate film and an organic thin film, a resist upper layer film 5 using a photoresist material is formed. Then, as Figure 2 (H), the exposed portion 6 of the resist upper film is subjected to pattern exposure. Figure 2(I) is developed with a developer to form a resist upper film pattern 5a on the resist upper film. Figure 2 (J), using the patterned resist upper film as a mask, dry etching is performed on the resist intermediate film or on the organic thin film and the inorganic hard mask intermediate film to transfer the pattern, thereby forming a resist intermediate film pattern 4a or an inorganic hard mask intermediate film pattern. Then, as Figure 2 (K), using the resist intermediate film or inorganic hard mask intermediate film with the transferred pattern as a mask, dry etching is performed on the resist lower film transfer pattern to form a resist lower film pattern 7a. Then, as Figure 2 (L), the metal-containing film 8 is coated on the resist underlayer film having been patterned using the metal-containing film-forming composition, and the space between the resist underlayer film patterns 7a is filled with the metal-containing film 8. Then, the metal-containing film coated on the resist underlayer film having been patterned is etched back by a chemical stripper or dry etching, as shown in FIG. Figure 2 Then, the resist intermediate film 4a or the hard mask intermediate film remaining on the top surface of the resist lower film pattern 7a is removed by dry etching, as shown in FIG. Figure 2 Then, the exposed surface of the resist lower film pattern 7a is removed by dry etching. Figure 2 (O) to obtain a metal-containing film having a reverse pattern 8a of the original pattern. Figure 2 (P), using the metal-containing film having the reverse pattern formed thereon as a mask, the aforementioned processed layer 2 is processed to form a reverse pattern 2b on the aforementioned processed layer of the processed substrate.

[0532] As described above, when forming the resist underlayer film on the substrate to be processed, the resist underlayer film can be formed by a method using a coating type organic underlayer film material, a CVD method, an ALD method, etc. The coating type organic underlayer film material is disclosed in, for example, Japanese Patent Laid-Open No. 2012-1687, Japanese Patent Laid-Open No. 2012-77295, Japanese Patent Laid-Open No. 2004-264710, Japanese Patent Laid-Open No. 2005-043471, Japanese Patent Laid-Open No. 2005-250434, Japanese Patent Laid-Open No. 2007-293294, Japanese Patent Laid-Open No. 2008-65303. Gazette, Japanese Patent Application Publication No. 2004-205685, Japanese Patent Application Publication No. 2007-171895, Japanese Patent Application Publication No. 2009-14816, Japanese Patent Application Publication No. 2007-199653, Japanese Patent Application Publication No. 2008-274250, Japanese Patent Application Publication No. 2010-122656, Japanese Patent Application Publication No. 2012-214720, Japanese Patent Application Publication No. 2 014-29435, 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 Publication No. 2005-128509, Japanese Resins and compositions disclosed in JP-A-2006-259249, JP-A-2006-259482, JP-A-2006-293298, JP-A-2007-316282, JP-A-2012-145897, JP-A-2017-119671, JP-A-2019-44022, and the like.

[0533] In the above tone reversal pattern forming method, after the obtained resist underlayer film pattern is coated with a metal-containing film-forming composition, in order to expose the top surface of the resist underlayer film pattern, it is preferred to remove the metal-containing film using a dry etching gas mainly composed of a chlorine-based gas. Thereafter, the resist intermediate film or hard mask intermediate film remaining on the resist underlayer film is removed by dry etching using a fluorine-based gas, and the exposed resist underlayer film pattern is removed by dry etching using an oxygen-based gas, thereby forming a metal-containing film pattern.

[0534] In the above-mentioned tonal reversal pattern forming method, it is preferred 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 and / or flattening properties, and can form a flat hardened film even if the processed film has a structure or height difference (concave and convex) of more than 30nm in height. It is ideal that the height of the structure or height difference of the above-mentioned resist lower film pattern is more than 30nm, more preferably more than 50nm, and more preferably more than 100nm. In the method of reversing the resist lower film pattern having the above-mentioned height pattern, it is very ideal to perform the pattern reversal and transfer with high precision by forming a film of the metal-containing film-forming composition of the present invention for filling and flattening. Compared with the resist underlayer film using the known coating type organic underlayer material, the resist underlayer film using fluorocarbon gas has excellent dry etching resistance, 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.

[0535] Example

[0536] The present invention will be specifically described below using synthesis examples, comparative synthesis examples, examples, and comparative examples, but the present invention is not limited thereto.

[0537] [Synthesis example]

[0538] In the following synthesis examples and comparative synthesis examples, the following organic group raw material group G: (G1) to (G14) and silicon-containing organic group raw material group H: (H1) were used.

[0539] Raw material group G: (G1) to (G14) are as follows.

[0540] [Chemistry 60]

[0541]

[0542] The raw material group H: (H1) is as follows.

[0543] [Chemistry 61]

[0544]

[0545] As the metal source M, the following metal compounds were used.

[0546] (M1): Tetraisopropoxytitanium (Sigma-Aldrich Corp, 377996)

[0547] (M2): Butoxytitanium tetramer (Fuji Film Wako Pure Chemical Industries, Ltd.)

[0548] (M3): Zr(OBu)4: tetrabutoxyzirconium (IV) (80 mass % 1-butanol solution) (Tokyo Chemical Industry Co., Ltd., Z0016)

[0549] (M4): Hf(OBu)4: n-butoxyhafnium(IV) (Sigma-Aldrich Corp, 667943)

[0550] [Synthesis Example 1] Synthesis of Metal-Containing Film-Forming Compound (A-1)

[0551] Under nitrogen atmosphere, add 1.6 g of deionized water and 54.5 g of n-butanol solution to 40.5 g of n-butanol solution of 28.4 g of tetraisopropoxytitanium (M1) at room temperature for 2 hours while stirring. Hydrolysis and condensation of metal compound M1 are thereby performed. 26.4 g of organic group raw material (G1) is added to the obtained solution, and stirred at room temperature for 30 minutes. After concentrating the solution at 30°C under reduced pressure, heat it to 60°C, and continue heating under reduced pressure until no distillate appears. At the point when no distillate is seen, add 69.0 g of PGMEA / PGME (weight ratio 70 / 30) solution, and heat it at 40°C under reduced pressure until IPA no longer distills out, to obtain a PGMEA / PGME solution of metal-containing film-forming compound (A-1). The concentration of components other than the solvent in the above solution is 20% by mass.

[0552] [Synthesis Examples 2 to 12 and Comparative Synthesis Examples 13 to 16] Synthesis of Metal-Containing Film-Forming Compounds (A-2) to (A-12) and Comparative Metal-Containing Film-Forming Compounds (R-1) to (R-4)

[0553] According to the feed amount shown in Table 1, one of the above-mentioned metal sources M and one or two of the above-mentioned compound group G are used, and otherwise the same reaction conditions as in Synthesis Example 1 are followed to obtain the metal-containing film-forming compounds (A-2) to (A-12) shown in Table 1 and the metal-containing film-forming compounds (R-1) to (R-4) for comparative examples.

[0554] [Table 1]

[0555]

[0556] [Comparative Synthesis Example 17] Synthesis of a Metal-Containing Film-Forming Compound (R-5) for Comparative Use

[0557] Under a nitrogen environment, 48.0 g of tetrabutoxyzirconium (IV) (80% by mass 1-butanol solution) (M3) was dissolved in 59.4 g of PGMEA / PGME (weight ratio 70 / 30) solution, and the reaction temperature was raised to 50°C while stirring, and 20.4 g of compound H1 was added dropwise to the above solution. After the addition, the reaction temperature was set to 60°C and stirring was continued for 2 hours. Then, a mixture of 29.6 g of compound G9 suspended in 24.8 g of PGMEA / PGME (weight ratio 70 / 30) solution was added to the above reaction system, and the reaction temperature was maintained at 60°C and stirring was continued for 1 hour. After cooling to room temperature, the obtained reaction solution was filtered with a 0.45 μm PTFE filter to obtain a PGMEA / PGME solution of a comparative metal-containing film-forming compound (R-5). The concentration of components other than the solvent in the above solution was 21% by mass.

[0558] [Table 2]

[0559]

[0560] [Synthesis of Organic Film-Forming Resin (R-6) for Comparative Example]

[0561] 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, a pre-mixed and 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 completed, 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. 300 g of THF was added to the residue to make a uniform solution, and then crystallized in 2,000 g of hexane. The precipitated crystals were separated by filtration, washed twice with 500 g of hexane and recovered. The recovered crystals were vacuum dried at 70°C to obtain resin (R-6).

[0562] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent, and the following results were obtained.

[0563] (R-6): Mw=3,300, Mw / Mn=2.54

[0564] [Chemistry 62]

[0565]

[0566] (Synthesis of Flowability Improver)

[0567] The fluidity enhancer was synthesized using the following organic group raw material group G: (G19) to (G21) and the modifying agent K: (K1) to (K2).

[0568] Organic group raw material group G: (G19) to (G21) are shown below.

[0569] [Chemistry 63]

[0570]

[0571] Modifying agents K: (K1) to (K2) are shown below.

[0572] [Chemistry 64]

[0573]

[0574] [Synthesis of fluidity enhancer (BPA-1)]

[0575] Under nitrogen atmosphere, add 45.5 g of the compound (G19) of the organic group raw material group G, 9.8 g of potassium carbonate, and 150 g of DMF to prepare a uniform dispersion at an internal temperature of 50°C. Slowly add 17.6 g of the modifier (K1) and react at an internal temperature of 50°C for 24 hours. Add 300 ml of methyl isobutyl ketone and 300 g of pure water to the reaction solution to dissolve the precipitated salt, and then remove the separated water layer. After washing the organic layer 6 times with 100 g of 3% nitric acid aqueous solution and 100 g of pure water, the organic layer is dried under reduced pressure to obtain a fluidity promoter (BPA-1).

[0576] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the following results were obtained.

[0577] (BPA-1): Mw=965, Mw / Mn=1.08

[0578] [Chemistry 65]

[0579]

[0580] [Synthesis of fluidity enhancer (BPA-2)]

[0581] 80.0 g of the epoxy compound (G20) of the organic group raw material group G, 51.0 g of the modifying agent (K2), and 600 g of 2-methoxy-1-propanol were prepared into a uniform solution at an internal temperature of 100°C under a nitrogen atmosphere, and then 5.7 g of benzyltriethylammonium chloride was added and stirred at an internal temperature of 120°C for 12 hours. After cooling to room temperature, 1,500 g of methyl isobutyl ketone was added, and the organic layer was washed 5 times with 300 g of pure water. The organic layer was dried under reduced pressure to obtain a fluidity promoter (BPA-2).

[0582] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the following results were obtained.

[0583] (BPA-2): Mw=900, Mw / Mn=1.04

[0584] [Chemistry 66]

[0585]

[0586] [Synthesis of fluidity enhancer (BPA-3)]

[0587] Under nitrogen atmosphere, 20.0 g of the resin (G21) of the organic group raw material group G, 34.5 g of potassium carbonate, and 100 g of DMF were added to form a uniform dispersion at an internal temperature of 50°C. 23.8 g of the modifier (K1) was slowly added, and the reaction was carried out at an internal temperature of 50°C for 24 hours. 300 ml of methyl isobutyl ketone and 300 g of pure water were added to the reaction solution to dissolve the precipitated salt, and then 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 a fluidity promoter (BPA-3).

[0588] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0589] (BPA-3): Mw=9,400, Mw / Mn=3.59

[0590] [Chemistry 67]

[0591]

[0592] [Preparation of Metal-Containing Film-Forming Composition (MUL-1)]

[0593] The metal-containing film-forming compound (A-1) is dissolved in a mixed solvent ((B) organic solvent) of (D) surfactant FC-4430 (manufactured by Sumitomo 3M Co., Ltd.) containing 0.5 mass % of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) in the proportions shown in Table 3, and filtered with a 0.02 μm membrane filter to prepare a metal-containing film-forming composition (MUL-1).

[0594] [Preparation of Metal-Containing Film-Forming Compositions (MUL-2 to 18) and Metal-Containing Film-Forming Compositions for Comparative Examples (Comparative Examples MUL-1 to 6)]

[0595] The types and contents of each component are as shown in Table 3. The same operations as those for the preparation of the metal-containing film-forming composition (MUL-1) are performed to prepare each composition. In Table 3, "-" represents that the component is not used. The cross-linking agent is represented by the following formula (C-1). The acid generator (TAG) is represented by the following formula (E-1). The high boiling point solvent (B-1) is ethylene glycol dibenzyl ether: boiling point 364°C.

[0596] [Crosslinking agent, acid generator]

[0597] The cross-linking agent (C-1) and the acid generator (E-1) used in the metal-containing film-forming composition are shown below.

[0598] [Chemistry 68]

[0599]

[0600] [Chemistry 69]

[0601]

[0602] [Table 3]

[0603]

[0604] [Example 1 and Comparative Example 1: Evaluation of Landfill Characteristics]

[0605] The prepared compositions (MUL-1 to 18, and comparative examples MUL-1 to 6) were respectively coated on a SiO2 wafer substrate (substrate A) with a dense line & space pattern (line width 60nm, line depth 100nm, and distance between the centers of two adjacent lines 120nm), and heated at 350°C for 60 seconds using a hot plate to form a metal-containing film with a thickness of 80nm.

[0606] Furthermore, the above-prepared compositions (MUL-1~18, and comparative examples MUL-1~6) were respectively coated on a SiO2 wafer substrate (substrate B) having a dense line & space pattern (line width 40nm, line depth 120nm, and distance between the centers of two adjacent lines 80nm), and heated at 350°C for 60 seconds using a hot plate to form a metal-containing film with a film thickness of 80nm.

[0607] The substrates A and B used are Figure 3The base substrate 9 (SiO2 wafer substrate) has a dense line & space pattern as shown in (Q) (bird's-eye view) and (R) (cross-sectional view). The cross-sectional shape of each wafer substrate obtained by the fill evaluation was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. to confirm whether there are pores (voids) inside the metal-containing film between the filling lines. The results are shown in Table 4. When a metal-containing film-forming composition with poor fill characteristics is used, pores appear inside the metal-containing film between the filling lines in this evaluation. When a metal-containing film-forming composition with good fill characteristics is used, in this evaluation, Figure 3 As shown in (S), the metal-containing film 10 without pores is filled inside the metal-containing film filling the lines of the base substrate 9 having a dense line & space pattern.

[0608] [Table 4]

[0609]

[0610]

[0611] As shown in Table 4, in Examples 1-1 to 1-18 using the metal-containing film-forming composition (MUL-1 to 18) of the present invention, no voids occurred in the respective substrates even after baking at 350°C, and dense line and space patterns could be filled, confirming that they still had good filling properties under high-temperature baking conditions.

[0612] On the other hand, in Comparative Examples 1-1 and 1-2 using comparative metal-containing film-forming compositions (Comparative Examples MUL-1 and MUL-2) containing metal-containing film-forming compounds having organic ligands without crosslinking groups of formulae (a-1) to (a-4) unlike the metal-containing film-forming compounds of the present invention, voids were observed at the bottom of the pattern after baking at 350° C. for both substrates A and B. It is presumed that these comparative metal-containing film-forming compositions had low heat resistance of the metal-containing film and that voids were generated due to large volume shrinkage caused by high-temperature baking.

[0613] On the other hand, in Comparative Examples 1-3 to 5 using comparative metal-containing film-forming compositions containing metal-containing film-forming compounds containing crosslinking groups of formulae (a-1) to (a-4) but not containing ligands derived from the organic compound represented by formula (1) (Comparative Examples UDL-3 to 5), substrate A was able to fill dense line & space patterns without voids, but voids were confirmed on substrate B containing finer patterns. It is speculated that these comparative metal-containing film-forming compositions contain crosslinking groups of formulae (a-1) to (a-4) but do not contain ligands derived from the organic compound represented by formula (1) of the present invention, and as a result, the heat resistance is insufficient, and voids are generated on substrate B containing finer patterns that are more susceptible to heat from the substrate.

[0614] [Example 2 and Comparative Example 2: Evaluation of Flattening Characteristics]

[0615] The flatness evaluation was performed using the substrate B used in the above-mentioned filling evaluation. Figure 4 The dense line & space pattern of the base substrate 11 (SiO2 wafer substrate) shown in (T) is observed using a scanning electron microscope (SEM) as shown in Figure 4 As shown in (U), the cross-sectional shape of each wafer substrate in which no voids were observed in the above-mentioned filling evaluation after baking at 350°C, and the height difference of the filling film 12 between the line pattern dense part and the non-line pattern forming part was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. ( Figure 4 The results are shown in Table 5. In this evaluation, the smaller the height difference, the better the flattening characteristics.

[0616] [Table 5]

[0617]

[0618] As shown in Table 5, Examples 2-1 to 2-18 using the metal-containing film-forming composition (MUL-1 to 18) of the present invention have a small height difference between the patterned portion and the non-patterned portion of the film, and it can be seen that they have comparable planarization performance to Comparative Example 2-1 using an organic resist underlayer film material. In addition, MDL-14 to which a high boiling point solvent (B-1) is added, and MDL-16 to 18 to which a fluidity promoter (BPA-1 to 3) is added show better planarization properties than the composition without additives. It is speculated that by using additives, the thermal fluidity of the metal-containing film-forming composition can be further improved. On the other hand, the metal-containing film-forming compound (A-1) containing only ligands from the organic compound represented by formula (1) is compared with the metal-containing film-forming compound (A-9) containing ligands other than ligands from the organic compound represented by formula (1), and excellent planarity is observed.

[0619] [Example 3 and Comparative Example 3: Etching Resistance Evaluation]

[0620] The metal-containing film-forming composition (MUL-1 to 18, and comparative examples MUL-1 to 6) was coated on a silicon substrate, and heated at 350°C for 60 seconds using a hot plate to form a metal-containing film with a thickness of 80 nm, and the film thickness a was measured. Then, each etching (condition 1 and condition 2) using CF4 gas was performed under the following conditions using an etching device TE8500 manufactured by Tokyo Electron, and the film thickness b was measured. From the film thickness etched during a specified time (film thickness a-film thickness b), the film thickness etched in 1 minute was calculated and defined as the etching rate (nm / min).

[0621] Under condition 1, the etching rate was rated as "very good (A)" when it was 50nm / min or less, "good (B)" when it was 50nm / min to 60nm / min, and "poor (C)" when it was greater than 60nm / min. Under condition 2, the etching rate was rated as "very good (A)" when it was 35nm / min or less, "good (B)" when it was 35nm / min to 40nm / min, and "poor (C)" when it was greater than 40nm / min. The results are shown in Table 6.

[0622] Dry etching conditions 1

[0623] Pressure: 200mT

[0624] RF power: 300W

[0625] CF4 gas flow rate: 100sccm

[0626] Time: 20 seconds

[0627] Dry etching conditions 2

[0628] Pressure: 160mT

[0629] RF power: 1000W

[0630] CF4 gas flow rate: 20sccm

[0631] Ar gas flow rate: 1000sccm

[0632] Time: 60 seconds

[0633] [Table 6]

[0634]

[0635] As shown in Table 6, Examples 3-1 to 3-18 using the metal-containing film-forming composition (MUL-1 to 18) of the present invention show excellent etching resistance to CF4 gas, compared with Comparative Example 3-6 using an organic lower film material (Comparative Example 3-6 using a metal-containing film-forming compound (R-6)). In addition, Comparative Example 3-5 using a non-hydrolyzed and condensed metal-containing film-forming compound (R-5) showed excellent dry etching resistance. In particular, the metal-containing film-forming composition (MUL-1 to 18) of the present invention still obtained a result showing high resistance under Condition 2 with a large Ar flow rate. Therefore, it can be considered that it also shows excellent resistance to physical etching with a large Ar flow rate used for etching oxide films of cutting-edge devices.

[0636] The metal-containing film-forming compound (A-9) containing ligands other than the ligands derived from the organic compound represented by formula (1) showed improved dry etching resistance compared to the metal-containing film-forming compound (A-1) containing only ligands derived from the organic compound represented by formula (1). That is, the present invention can appropriately adjust the dry etching resistance and planarization characteristics according to the required characteristics of the use process by adjusting the ratio of the ligands derived from the organic compound represented by formula (1) contained in the metal-containing film-forming compound.

[0637] [Example 4 and Comparative Example 4: Pattern Formation Method]

[0638] The above-mentioned metal-containing film-forming compositions (MUL-1 to 18, comparative example MUL-6) are coated on a SiO2 wafer substrate having a groove pattern (groove width 10μm, groove depth 0.10μm), and fired at 350°C for 60 seconds in the atmosphere to form a metal-containing film with a thickness of 80nm. A silicon-atom-containing resist intermediate film material (SOG-1) is coated thereon, and baked at 220°C for 60 seconds to form a resist intermediate film with a thickness of 50nm, and an ArF single-layer resist of a resist upper film material is coated thereon, and baked at 105°C for 60 seconds to form a photoresist film with a thickness of 100nm. A wet protection film material (TC-1) is coated on the photoresist film, and baked at 90°C for 60 seconds to form a protective film with a thickness of 50nm.

[0639] The silicon-containing resist interlayer material (SOG-1) was prepared in the following manner. First, a polymer represented by ArF silicon-containing interlayer polymer (SiP1) and a thermal crosslinking catalyst (CAT1) were dissolved in an organic solvent containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 7. The mixture obtained in this manner was filtered through a fluororesin filter having a pore size of 0.1 μm to prepare the silicon-containing resist interlayer material (SOG-1).

[0640] [Table 7]

[0641]

[0642]

[0643] The structural formulas of the ArF silicon-containing intermediate film polymer (SiP1) and the thermal crosslinking catalyst (CAT1) used are shown below.

[0644] [Chemistry 70]

[0645]

[0646] The resist upper film material (ArF single-layer resist) was prepared as follows: First, a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) were dissolved in a solvent containing 0.1% by mass of a surfactant FC-4430 (manufactured by Sumitomo 3M Co., Ltd.) according to the ratio shown in Table 8, and filtered through a 0.1 μm fluororesin filter to prepare a resist upper film material.

[0647] [Table 8]

[0648]

[0649] The polymer (RP1), the acid generator (PAG1), and the basic compound (Amine1) used for the resist upper layer film material (single-layer resist for ArF) are shown below.

[0650] [Chemistry 71]

[0651]

[0652] The wet protective film material (TC-1) was prepared by dissolving the protective film polymer (PP1) in an organic solvent according to the ratio shown in Table 9 and filtering the solution with a 0.1 μm fluororesin filter.

[0653] [Table 9]

[0654]

[0655] The protective film polymer (PP1) used in the wet protective film material (TC-1) is shown below.

[0656] [Chemistry 72]

[0657]

[0658] Next, the sample was exposed with an ArF immersion exposure apparatus (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% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain a 55nm1:1 positive line and space pattern (resist upper film pattern).

[0659] Next, the resist intermediate film was etched by dry etching using the resist upper film pattern as a mask to form a hard mask pattern, the metal-containing film was etched using the obtained hard mask pattern as a mask to form a metal-containing film pattern, and the SiO2 film was etched using the obtained metal-containing film pattern as a mask. Etching was performed using an etching apparatus CE-300I manufactured by ULVAC under the following conditions.

[0660] Transfer conditions of the resist upper layer film pattern to the resist intermediate film.

[0661] Dry etching conditions of CF4 gas

[0662] Pressure: 1Pa

[0663] Antenna RF power: 100W

[0664] Bias RF power: 15W

[0665] CF4 gas flow rate: 15sccm

[0666] Time: 60 seconds

[0667] Transfer conditions of hard mask pattern to metal-containing film.

[0668] Dry etching conditions of Cl2 gas

[0669] Pressure: 1Pa

[0670] Antenna RF power: 320W

[0671] Bias RF power: 30W

[0672] Cl2 gas flow rate: 25sccm

[0673] Time: 45 seconds

[0674] Transfer conditions of metal-containing film patterns to SiO2 films.

[0675] Dry etching conditions of CF4 gas

[0676] Pressure: 1Pa

[0677] Antenna RF power: 100W

[0678] Bias RF power: 15W

[0679] CF4 gas flow rate: 15sccm

[0680] Time: 60 seconds

[0681] The pattern cross section was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. The results are shown in Table 10.

[0682] [Table 10]

[0683]

[0684]

[0685] As shown in Table 10, in Examples 4-1 to 4-18 using the metal-containing film-forming composition (MUL-1 to 18) of the present invention, the resist upper film pattern was finally well transferred to the substrate, confirming that the metal-containing film-forming composition of the present invention is suitable for use in micro-processing using a multilayer resist method. On the other hand, in Comparative Example 4-1, which was found to have insufficient performance in dry etching resistance evaluation, the pattern shape was twisted during pattern processing, and ultimately a good pattern could not be obtained.

[0686] [Example 5 and Comparative Example 5: SOC pattern reversal method]

[0687] A coating type resist lower film material (SOC-1) as a resist lower film is applied to a silicon wafer substrate on which a SiO2 film has been formed, and baked at 350°C for 60 seconds to form a resist lower film with a film thickness of 150nm. A resist intermediate film material (SOG-1) containing silicon atoms is applied thereon, and baked at 220°C for 60 seconds to form a resist intermediate film with a film thickness of 40nm. An ArF single-layer resist for a resist upper film material is applied thereon, and baked at 105°C for 60 seconds to form a photoresist film with a film thickness of 100nm. A wet protection film material (TC-1) is applied to the photoresist film, and baked at 90°C for 60 seconds to form a protection film with a film thickness of 50nm.

[0688] The resist intermediate film material (SOG-1) containing silicon atoms, the resist upper film material (single-layer resist for ArF), and the wetting protective film material (TC-1) on the photoresist film use the same materials as those used in the above-mentioned pattern forming method (Example 4).

[0689] As for the coating type anti-etching underlayer film material (SOC-1), the polymer represented by the polymer for the resist underlayer film (SOP1) is dissolved in an organic solvent containing 0.1% by mass of FC-4430 (produced by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 11, and filtered with a fluororesin filter with a pore size of 0.2 μm to prepare the coating type anti-etching underlayer film material (SOC-1).

[0690] [Table 11]

[0691]

[0692] The structural formula of the polymer (SOP1) used for the resist underlayer film is shown in Table 12.

[0693] [Table 12]

[0694]

[0695] Secondly, it was exposed with 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 line and space pattern (resist upper film pattern).

[0696] Next, using a Tokyo Electron etching apparatus Telius, dry etching was performed to etch the resist intermediate film using the resist upper film pattern as a mask to form a hard mask pattern, and the resist lower film (SOC-1) was etched using the obtained hard mask pattern as a mask to form a SOC-1 film pattern. The etching conditions are as follows.

[0697] Transfer conditions of the resist upper layer film pattern to the resist intermediate film.

[0698] Chamber pressure: 50mT

[0699] RF power (upper): 500W

[0700] RF power (lower): 300W

[0701] CF4 gas flow rate: 150sccm

[0702] CHF3 gas flow rate: 50sccm

[0703] Time: 20 seconds

[0704] Transfer conditions of the hard mask pattern to the resist underlayer film.

[0705] Chamber pressure: 10mT

[0706] RF power (upper): 1,000W

[0707] RF power (lower): 300W

[0708] CO2 gas flow rate: 150sccm

[0709] CO gas flow rate: 50sccm

[0710] N2 gas flow rate: 50sccm

[0711] H2 gas flow rate: 150sccm

[0712] Time: 90 seconds

[0713] Next, the above-mentioned metal-containing film-forming composition (MUL-1 to 18, comparative examples MUL-1 to 2) is coated on the obtained SOC-1 film pattern, and fired at 350°C for 60 seconds in the atmosphere to form a metal-containing film with a thickness of 80 nm. Thereafter, the metal-containing film covering the SOC-1 film pattern is etched to expose the top surface of the SOC-1 film pattern. The resist intermediate film remaining on the surface of the SOC-1 film pattern exposed on the top surface is removed by etching, and then the exposed SOC-1 film pattern is removed by etching, and the above-mentioned pattern is reversed on the metal-containing film, and the obtained metal-containing film pattern is used as a mask to perform etching processing of the SiO2 film. As a comparative example, etching of the SiO2 film is also performed without using the metal-containing film-forming composition but using the SOC-1 film pattern as a mask (Comparative Example 5-3). The etching conditions are as shown below.

[0714] Etch-back conditions of the metal-containing film (exposure of the SOC-1 film pattern).

[0715] Pressure: 1Pa

[0716] Antenna RF power: 320W

[0717] Bias RF power: 30W

[0718] Cl2 gas flow rate: 25sccm

[0719] Time: 20 seconds

[0720] Removal of the resist intermediate film remaining on the SOC-1 film pattern.

[0721] Dry etching conditions of CF4 gas

[0722] Pressure: 1Pa

[0723] Antenna RF power: 100W

[0724] Bias RF power: 15W

[0725] CF4 gas flow rate: 15sccm

[0726] Time: 45 seconds

[0727] Removal of SOC-1 film pattern.

[0728] O2 gas dry etching conditions

[0729] Pressure: 1Pa

[0730] Antenna RF power: 300W

[0731] Bias RF power: 0W

[0732] O2 gas flow rate: 25sccm

[0733] Time: 35 seconds

[0734] Transfer conditions of metal-containing film patterns to SiO2 films.

[0735] Dry etching conditions of CF4 gas

[0736] Pressure: 1Pa

[0737] Antenna RF power: 100W

[0738] Bias RF power: 15W

[0739] CF4 gas flow rate: 15sccm

[0740] Time: 60 seconds

[0741] Comparative Example 5-3: Transfer conditions of SOC-1 film pattern to SiO2 film.

[0742] Dry etching conditions of CF4 gas

[0743] Pressure: 1Pa

[0744] Antenna RF power: 100W

[0745] Bias RF power: 15W

[0746] CF4 gas flow rate: 15sccm

[0747] Time: 60 seconds

[0748] The pattern cross section was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. The results are shown in Table 13.

[0749] [Table 13]

[0750]

[0751]

[0752] As shown in Table 13, in Examples 5-1 to 5-18 using the metal-containing film-forming composition (MUL-1 to 18) of the present invention, the SOC-1 film pattern was reversed with good accuracy, and the reversed pattern was finally well transferred to the substrate without pattern collapse. It can be confirmed that the metal-containing film-forming composition of the present invention is suitable for use in micro-processing using a tonality reversal etching method in a multilayer resist processing method. On the other hand, in Comparative Example 5-3, in which the SOC-1 film pattern was directly transferred to the SiO2 film, the etching resistance of the SOC-1 film was insufficient, and thus the distortion of the pattern shape was confirmed. In addition, the evaluation of the filling characteristics (substrate B) confirmed that the performance of Comparative Examples 5-1 to 5-2 was insufficient, and the metal-containing film was not filled to the bottom between the SOC-1 film patterns, so the pattern failed to reverse, and ultimately a good reverse pattern could not be obtained.

[0753] From the above, it can be seen that if the metal-containing film-forming composition contains the metal-containing film-forming compound of the present invention, it is extremely useful as a metal-containing layer (resist underlayer film) material used in the multilayer resist method and a reversal agent used in the tonal reversal etching method because it combines high-degree filling and flattening characteristics with dry etching resistance. Moreover, the pattern forming method of the present invention using it can form a fine pattern with high precision even if the processed body is a substrate with height differences.

[0754] This specification includes the following aspects.

[0755] [1] A metal-containing film-forming compound, which is (A) a metal-containing film-forming compound,

[0756] The aforementioned (A) metal-containing film-forming compound is a compound derived from a metal-containing compound obtained by hydrolyzing or condensing a metal compound represented by the following formula (A-1), or by hydrolyzing and condensing the metal compound, and further has a ligand derived from an organic compound represented by the following formula (1):

[0757] M(OR 1A )4 (A-1)

[0758] R 2A COXCOOH (1)

[0759] Wherein, M is Ti, Zr, or Hf, R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A It is a divalent organic group having 2 to 20 carbon atoms and containing at least one crosslinking group represented by any of the following general formulae (a-1) to (a-4), and X is a divalent organic group having 2 to 20 carbon atoms.

[0760] [Chemistry 73]

[0761]

[0762] In the above general formulas (a-1) to (a-4), R a is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding portion.

[0763] [2] The metal-containing film-forming compound according to [1], wherein

[0764] The aforementioned (A) metal-containing film-forming compound is

[0765] A metal-containing compound selected from one or more of a hydrolyzate of a metal compound represented by the aforementioned formula (A-1), a condensate of a metal compound represented by the aforementioned formula (A-1), and a hydrolysis-condensation product of a metal compound represented by the aforementioned formula (A-1), and a reaction product of an organic compound represented by the aforementioned formula (1).

[0766] [3] The metal-containing film-forming compound according to [1] or [2], wherein in the above formula (1), R 2A The structure represented by the following general formula (B-1):

[0767] [Chemistry 74]

[0768]

[0769] In the above general formula (B-1), R A1 is the structure represented by the above general formula (a-1), R A2 is any of the structures represented by the above general formula (a-2) or (a-3), Z is an oxygen atom or a secondary amine, L is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R A3 It is a saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, t is 1 to 6, s is 0 to 5, t+s is 1 to 6, r is 1 to 10, u is 0 or 1, m is 0 or 1, and * represents a bond to the carbon atom of the carbonyl group.

[0770] [4] The metal-containing film-forming compound according to any one of [1] to [3], wherein in the formula (1), the organic group X is a saturated hydrocarbon group having 2 to 20 carbon atoms or an unsaturated hydrocarbon group having 2 to 20 carbon atoms.

[0771] [5] The metal-containing film-forming compound according to any one of [1] to [4], wherein in the above formula (1), the above organic group X is a group represented by any one of the following formulas (2):

[0772] [Chemistry 75]

[0773]

[0774] In the above general formula (2), R a and R b is a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, R c is a hydrogen atom or a monovalent organic group having 1 to 17 carbon atoms, R a and R b They may be bonded to form a cyclic substituent. *1 and *2 each represent a bond to the carbonyl group, and *1 and *2 may be reversed.

[0775] [6] The metal-containing film-forming compound according to any one of [1] to [5], wherein the metal-containing film-forming compound (A) comprises a compound having a structure represented by the following general formula (m-1):

[0776] [Chemistry 76]

[0777]

[0778] In the above formula (m-1), R ae ~R de Each independently represents R in the above formula (A-1) 1A Or COXCOR in the above formula (1) 2A Any one of R ae ~R de At least one of them is COXCOR in the above formula (1) 2A , n is 1 to 20, and M is the same as M in the above formula (A-1).

[0779] [7] The metal-containing film-forming compound according to any one of [1] to [5], wherein

[0780] The metal-containing film-forming compound (A) contains, in addition to the ligands derived from the organic compound represented by the above formula (1), at least one additional ligand selected from the group consisting of ligands derived from an organic compound represented by the following formula (3) and ligands derived from any of succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride.

[0781] The aforementioned additional ligand does not contain a group represented by the above general formulae (a-1) to (a-4),

[0782] R 3A COOH(3)

[0783] In the formula, R 3A It is a monovalent organic group having 1 to 20 carbon atoms.

[0784] [8] The metal-containing film-forming compound according to [7], wherein the metal-containing film-forming compound (A) comprises a compound having any of the following structures:

[0785] [Chemistry 77]

[0786]

[0787] The above R 3a is a monovalent organic group having 1 to 20 carbon atoms and not containing a crosslinking group represented by the above general formulae (a-1) to (a-4), or any of the following structures, R 1A Same as R in the above formula (A-1) 1A , R 2A Same as R in formula (1) 2A , n is 1 to 20, M is the same as M in the above formula (A-1),

[0788] [Chemistry 78]

[0789]

[0790] In the above formula, R 3b It is an alkyl group having 1 to 10 carbon atoms, and * represents a bonding portion to the carbonyl carbon.

[0791] [9] A metal-containing film-forming composition comprising:

[0792] (A) a metal-containing film-forming compound according to any one of [1] to [8] and

[0793] (B) Organic solvent.

[0794]

[10] The metal-containing film-forming composition according to [9], wherein

[0795] The aforementioned composition further comprises

[0796] (C) a cross-linking agent,

[0797] (D) surfactant, and

[0798] (E) Acid generator

[0799] One or more of the following.

[0800]

[11] The metal-containing film-forming composition according to [9] or

[10] , wherein

[0801] The (B) organic solvent contains (B-1) a high boiling point solvent, and the (B-1) high boiling point solvent is one or more organic solvents having a boiling point of 180 degrees or higher.

[0802]

[12] The metal-containing film-forming composition according to any one of [9] to

[11] , wherein the metal-containing film-forming composition further comprises a fluidity promoter (BP) having an organic group represented by the following general formula (bp1a) and an aromatic ring,

[0803] [Chemistry 79]

[0804]

[0805] In the formula, * represents the bonding site to the oxygen atom, R B is a divalent organic group having 1 to 10 carbon atoms, R A It is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.

[0806]

[13] The metal-containing film-forming composition according to

[12] , wherein the fluidity promoter (BP) has at least one structural unit represented by any of the following general formulae (BP-1), (BP-2), (BP-3), (BP-4) and (BP-5),

[0807] [Chemistry 80]

[0808]

[0809] In the above general formulae (BP-1) and (BP-2), W1 and W2 are each independently a benzene ring or a naphthalene ring, and the hydrogen atoms in the benzene ring and the naphthalene ring may be substituted by a hydrocarbon group having 1 to 6 carbon atoms. a1 is a group represented by the following general formula (4). Y is a group represented by the following general formula (5). n1 is 0 or 1, n2 is 1 or 2, and V each independently represents a hydrogen atom or a linking part.

[0810] [Chemistry 81]

[0811]

[0812] In the above general formula (BP-3), Z1 is a group represented by the following general formula (6), R a1 It is the following general formula (4): n4 is 0 or 1, n5 is 1 or 2, and V each independently represents a hydrogen atom or a linking part.

[0813] [Chemistry 82]

[0814]

[0815] * indicates a bonding portion with an oxygen atom.

[0816] [Chemistry 83]

[0817]

[0818] * indicates an atomic bond.

[0819] [Chemistry 84]

[0820]

[0821] In the above general formula (6), W1, W2, Y and n1 are the same as described above.

[0822] [Chemistry 85]

[0823]

[0824] In the formula, m3 and m4 represent 1 or 2, and Z2 represents a single bond or any of the structures represented by the following general formula (7). x It is any of the structures represented by the following general formula (8).

[0825] [Chemistry 86]

[0826]

[0827] In the formula, * represents an atomic bond, l represents an integer from 0 to 3, and R az ~R fz Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with fluorine, a phenyl group, or a phenylethyl group, and R az With R bz They can also form cyclic compounds.

[0828] [Chemistry 87]

[0829]

[0830] In the formula, * represents a bonding site to an aromatic ring, and Q1 is a linear saturated hydrocarbon group having 1 to 30 carbon atoms, or a structure represented by the following general formula (9).

[0831] [Chemistry 88]

[0832]

[0833] In the formula, * represents the bonding site to the carbonyl group, R i It is the above general formula (4). j It represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. 3z and n 4z represents the number of substituents on the aromatic ring, and each represents an integer from 0 to 7. 3z +n 4z It is between 0 and 7. 5z Represents 0 to 2.

[0834] [Chemistry 89]

[0835]

[0836] In the above general formula (BP-5), R 1is a saturated monovalent organic group having 1 to 30 carbon atoms or an unsaturated monovalent organic group having 2 to 30 carbon atoms, X1 is a divalent organic group having 1 to 30 carbon atoms, R a1 It is the above-mentioned general formula (4). P is an integer of 0 to 5, q1 is an integer of 1 to 6, p+q1 is an integer of 1 to 6, and q2 is 0 or 1.

[0837]

[14] A method for producing (A) a metal-containing film-forming compound, characterized by comprising the following steps:

[0838] reacting an organic compound represented by the following formula (1) with one or more selected from the group consisting of a hydrolyzate of a metal compound represented by the following formula (A-1), a condensate of a metal compound represented by the following formula (A-1), and a hydrolysis-condensate of a metal compound represented by the following formula (A-1) or more thereof; or

[0839] The metal compound represented by the following general formula (A-2) is hydrolyzed or condensed, or hydrolyzed and condensed,

[0840] M(OR 1A )4 (A-1)

[0841] R 2A COXCOOH (1)

[0842] Wherein, M is Ti, Zr, or Hf, R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A It is a divalent organic group having 2 to 20 carbon atoms and containing at least one crosslinking group represented by any of the following general formulae (a-1) to (a-4), and X is a divalent organic group having 2 to 20 carbon atoms.

[0843] [Chemistry 90]

[0844]

[0845] In the above general formulas (a-1) to (a-4), R a is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding portion.

[0846] (R 2A COXCOO x M(OR 1A ) y (A-2)

[0847] Wherein, M is Ti, Zr, or Hf, R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2AIt is a divalent organic group having 2 to 20 carbon atoms and containing at least one crosslinking group represented by the above general formulae (a-1) to (a-4), X is a divalent organic group having 2 to 20 carbon atoms, x+y=4, and x and y are integers greater than 1.

[0848]

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

[0849] (I-1) After applying the metal-containing film-forming composition as described in any one of [9] to

[13] on a substrate to be processed, forming a metal-containing film by heat treatment,

[0850] (I-2) forming a resist upper layer film on the aforementioned metal-containing film using a photoresist material,

[0851] (I-3) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0852] (I-4) using the patterned resist upper layer film as a mask to dry-etch the metal-containing film to transfer the pattern, and

[0853] (I-5) The substrate to be processed is processed using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0854]

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

[0855] (II-1) After applying the metal-containing film-forming composition as described in any one of [9] to

[13] on a substrate to be processed, forming a metal-containing film by heat treatment,

[0856] (II-2) forming a resist intermediate film on the aforementioned metal-containing film,

[0857] (II-3) forming a resist upper layer film on the resist intermediate film using a photoresist material,

[0858] (II-4) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0859] (II-5) using the patterned resist upper layer film as a mask, dry etching is performed to transfer the pattern to the resist intermediate layer film,

[0860] (II-6) using the resist intermediate film having the transferred pattern as a mask, dry etching the transferred pattern on the metal-containing film, and

[0861] (II-7) The substrate to be processed is processed using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0862]

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

[0863] (III-1) After applying the metal-containing film-forming composition as described in any one of [9] to

[13] on a substrate to be processed, forming a metal-containing film by heat treatment,

[0864] (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 aforementioned metal-containing film,

[0865] (III-3) forming an organic thin film on the aforementioned inorganic hard mask intermediate film,

[0866] (III-4) forming a resist upper layer film on the aforementioned organic thin film using a photoresist material,

[0867] (III-5) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0868] (III-6) using the patterned resist upper layer film as a mask, dry etching is performed to transfer the pattern to the organic thin film and the inorganic hard mask intermediate film,

[0869] (III-7) using the inorganic hard mask intermediate film having the transferred pattern as a mask, dry etching the transferred pattern on the metal-containing film, and

[0870] (III-8) The substrate to be processed is processed using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0871]

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

[0872] (IV-1) After applying the metal-containing film-forming composition as described in any one of [9] to

[13] on a substrate to be processed, forming a metal-containing film by heat treatment,

[0873] (IV-2) forming an organic intermediate film on the aforementioned metal-containing film,

[0874] (IV-3) forming a combination of an inorganic hard mask interlayer film selected from a resist interlayer film containing silicon or a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film and an organic thin film on the aforementioned organic interlayer film,

[0875] (IV-4) forming a resist upper layer film using a photoresist material on the aforementioned silicon-containing resist intermediate film or the aforementioned organic thin film,

[0876] (IV-5) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0877] (IV-6) using the patterned resist upper layer film as a mask, dry etching is performed to transfer the pattern to the silicon-containing resist intermediate film or the organic thin film and the inorganic hard mask intermediate film,

[0878] (IV-7) using the silicon-containing resist intermediate film or inorganic hard mask intermediate film to which the pattern has been transferred as a mask, and dry etching the pattern transferred on the organic intermediate film,

[0879] (IV-8) using the organic intermediate film having the transferred pattern as a mask to dry-etch the transferred pattern on the metal-containing film, and

[0880] (IV-9) The substrate to be processed is processed using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0881]

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

[0882] (V-1) forming a resist underlayer film on a substrate to be processed,

[0883] (V-2) forming a resist intermediate film, or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film and an organic thin film on the resist underlayer film,

[0884] (V-3) forming a resist upper layer film using a photoresist material on the aforementioned resist intermediate film or the combination of the inorganic hard mask intermediate film and the organic thin film,

[0885] (V-4) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0886] (V-5) using the patterned resist upper layer film as a mask, dry etching to transfer a pattern to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film,

[0887] (V-6) using the resist intermediate film or inorganic hard mask intermediate film to which the pattern has been transferred as a mask, dry etching is performed to transfer the pattern on the resist lower layer film,

[0888] (V-7) coating the metal-containing film-forming composition as described in any one of [9] to

[13] 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.

[0889] (V-8) etching back the metal-containing film covering the patterned resist underlayer film by chemical stripping agent or dry etching to expose the top surface of the patterned resist underlayer film,

[0890] (V-9) the resist intermediate film or the hard mask intermediate film remaining on the top surface of the resist lower layer film is removed by dry etching,

[0891] (V-10) removing the aforementioned patterned resist underlayer film exposed on the surface by dry etching to form a reverse pattern of the original pattern on the metal-containing film,

[0892] (V-11) The metal-containing film having the reverse pattern formed therein is used as a mask to process the substrate to be processed, thereby forming a reverse pattern on the substrate to be processed.

[0893] The present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are illustrative only, and any device having substantially the same configuration and exhibiting the same function and effect as the technical concept described in the claims of the present invention is included in the technical scope of the present invention.

[0894] Description of Reference Numerals

[0895] 1:Substrate

[0896] 1A: Processed substrate

[0897] 2: Processing layer

[0898] 2a: Pattern (forming a pattern on the processed layer)

[0899] 3: Metal-containing films

[0900] 3a: Metal-containing film pattern

[0901] 4: Anti-etching interlayer

[0902] 4a: Resist interlayer pattern

[0903] 5: Resist upper film

[0904] 5a: Resist upper film pattern

[0905] 6: Exposure part

[0906] 7: Resist lower layer film

[0907] 7a: Resist lower film pattern

[0908] 8:Metallic film

[0909] 8a: Metal-containing film pattern obtained by inverting the resist lower film pattern

[0910] 9: Base substrate with dense line & spacing

[0911] 10: Metal-containing resist underlayer film

[0912] 11: Base substrate with dense line & spacing

[0913] 12: Metal-containing resist underlayer film

[0914] Delta12: The height difference between the patterned part and the non-patterned part of the metal-containing resist lower layer film 12

Claims

1. A metal-containing film-forming compound, which is (A) a metal-containing film-forming compound, The (A) metal-containing film-forming compound is a compound derived from a metal compound represented by the following formula (A-1) by hydrolysis or condensation, or by hydrolysis and condensation, and further has a ligand derived from an organic compound represented by the following formula (1): M(OR 1A ) 4 (A-1) R 2A COXCOOH (1) Wherein, M is Ti, Zr, or Hf, R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A is a divalent organic group having 2 to 20 carbon atoms and containing at least one crosslinking group represented by any of the following general formulae (a-1) to (a-4), X is a divalent organic group having 2 to 20 carbon atoms, In the above general formulas (a-1) to (a-4), R a is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding portion.

2. The metal-containing film-forming compound according to claim 1, in, The (A) metal-containing film-forming compound is a metal-containing compound. A reaction product of an organic compound represented by the formula (1) and one or more selected from a hydrolyzate of a metal compound represented by the formula (A-1) alone, a condensate of a metal compound represented by the formula (A-1) alone, and a hydrolysis-condensation product of a metal compound represented by the formula (A-1) alone.

3. The metal-containing film-forming compound according to claim 1, in, In the formula (1), R 2A The structure represented by the following general formula (B-1): In the above general formula (B-1), R A1 is the structure represented by the above general formula (a-1), R A2 is any of the structures represented by the above general formula (a-2) or (a-3), Z is an oxygen atom or a secondary amine, L is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R A3 It is a saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, t is 1 to 6, s is 0 to 5, t+s is 1 to 6, r is 1 to 10, u is 0 or 1, m is 0 or 1, and * represents a bond to the carbon atom of the carbonyl group.

4. The metal-containing film-forming compound according to claim 1, in, In the formula (1), the organic group X is a saturated hydrocarbon group having 2 to 20 carbon atoms or an unsaturated hydrocarbon group having 2 to 20 carbon atoms.

5. The metal-containing film-forming compound according to claim 1, in, In the formula (1), the organic group X is a group represented by any of the following formulas (2): In the above general formula (2), R a and R b is a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, R c is a hydrogen atom or a monovalent organic group having 1 to 17 carbon atoms, R a and R b They may be bonded to form a cyclic substituent, and *1 and *2 each represent a bond to the carbonyl group, and *1 and *2 may be reversed.

6. The metal-containing film-forming compound according to claim 1, in, The (A) metal-containing film-forming compound contains a compound having a structure represented by the following general formula (m-1): In the above formula (m-1), R ae ~R de Each independently represents R in the above formula (A-1) 1A Or COXCOR in the above formula (1) 2A Any one of R ae ~R de At least one of them is COXCOR in the above formula (1) 2A , n is 1 to 20, and M is the same as M in the above formula (A-1).

7. The metal-containing film-forming compound according to claim 1, in, The metal-containing film-forming compound (A) contains, in addition to the ligands derived from the organic compound represented by the formula (1), at least one additional ligand selected from the group consisting of a ligand derived from an organic compound represented by the following formula (3) and a ligand derived from any of succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride. The additional ligand does not contain a group represented by the above general formulae (a-1) to (a-4), R 3A COOH(3) In the formula, R 3A It is a monovalent organic group having 1 to 20 carbon atoms.

8. The metal-containing film-forming compound according to claim 7, in, The (A) metal-containing film-forming compound includes a compound having any of the following structures, The above R 3a is a monovalent organic group having 1 to 20 carbon atoms and not containing a crosslinking group represented by the above general formulae (a-1) to (a-4), or any of the following structures, R 1A Same as R in the above formula (A-1) 1A , R 2A Same as R in formula (1) 2A , n is 1 to 20, M is the same as M in the above formula (A-1), In the above formula, R 3b It is an alkyl group having 1 to 10 carbon atoms, and * represents a bonding portion to the carbonyl carbon.

9. A metal-containing film-forming composition, characterized in that it contains: (A) a metal-containing film-forming compound according to any one of claims 1 to 8, and (B) Organic solvent.

10. The metal-containing film-forming composition according to claim 9, in, The composition further contains (C) a cross-linking agent, (D) surfactant, and (E) Acid generator One or more of the following.

11. The metal-containing film-forming composition according to claim 9, in, The (B) organic solvent contains (B-1) a high boiling point solvent, and the (B-1) high boiling point solvent is one or more organic solvents having a boiling point of 180 degrees or higher.

12. The metal-containing film-forming composition according to claim 9, in, The metal-containing film-forming composition further contains a fluidity promoter (BP) having an organic group represented by the following general formula (bp1a) and an aromatic ring, In the formula, * represents the bonding site to the oxygen atom, R B is a divalent organic group having 1 to 10 carbon atoms, R A It is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.

13. The metal-containing film-forming composition according to claim 12, in, The fluidity promoter (BP) has at least one structural unit represented by any of the following general formulae (BP-1), (BP-2), (BP-3), (BP-4) and (BP-5), In the general formulas (BP-1) and (BP-2), W 1 and W 2 Each independently represents a benzene ring or a naphthalene ring, and the hydrogen atoms in the benzene ring and the naphthalene ring may be substituted by a hydrocarbon group having 1 to 6 carbon atoms. a1 is a group represented by the following general formula (4), Y is a group represented by the following general formula (5), n 1 is 0 or 1, n 2 is 1 or 2, V each independently represents a hydrogen atom or a linking portion, In the above general formula (BP-3), Z 1 is a group represented by the following general formula (6), R a1 The following general formula (4), n 4 is 0 or 1, n 5 is 1 or 2, V each independently represents a hydrogen atom or a linking portion, * indicates the bond with oxygen atom, * indicates atomic bonds, In the above general formula (6), W 1 , W 2 , Y, n 1 As mentioned above, In the formula, m 3 and m 4 Indicates 1 or 2, Z 2 is a single bond or any of the structures represented by the following general formula (7), R x Any of the structures represented by the following general formula (8), In the formula, * represents an atomic bond, l represents an integer from 0 to 3, and R az ~R fz Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with fluorine, a phenyl group, or a phenylethyl group, and R az With R bz They can also bond to form cyclic compounds. In the formula, * represents the bonding site to the aromatic ring, Q 1 is a linear saturated hydrocarbon group having 1 to 30 carbon atoms, or a structure represented by the following general formula (9), In the formula, * represents the bonding site to the carbonyl group, R i is the above general formula (4), R j represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms, n 3z and n 4z represents the number of substituents on the aromatic ring, each representing an integer from 0 to 7, but n 3z +n 4z is greater than 0 and less than 7, n 5z Indicates 0 to 2, In the general formula (BP-5), R 1 is a saturated monovalent organic group having 1 to 30 carbon atoms or an unsaturated monovalent organic group having 2 to 30 carbon atoms, X 1 is a divalent organic group having 1 to 30 carbon atoms, R a1 is the above general formula (4), p is an integer from 0 to 5, q 1 is an integer from 1 to 6, p+q 1 is an integer from 1 to 6, q 2 Is 0 or 1.

14. A method for producing a (A) metal-containing film-forming compound, characterized by comprising the following steps: reacting an organic compound represented by the following formula (1) with one or more selected from the group consisting of a hydrolyzate of a metal compound represented by the following formula (A-1), a condensate of a metal compound represented by the following formula (A-1), and a hydrolysis-condensate of a metal compound represented by the following formula (A-1) or more thereof; or The metal compound represented by the following general formula (A-2) is hydrolyzed or condensed, or hydrolyzed and condensed, M(OR 1A ) 4 (A-1) R 2A COXCOOH (1) Wherein, M is Ti, Zr, or Hf, R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A is a divalent organic group having 2 to 20 carbon atoms and containing at least one crosslinking group represented by any of the following general formulae (a-1) to (a-4), X is a divalent organic group having 2 to 20 carbon atoms, In the above general formulas (a-1) to (a-4), R a is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, * represents a bonding part, (R 2A COXCOO) x M(OR 1A ) y (A-2) Wherein, M is Ti, Zr, or Hf, R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A It is a divalent organic group having 2 to 20 carbon atoms and containing at least one crosslinking group represented by the above general formulae (a-1) to (a-4), X is a divalent organic group having 2 to 20 carbon atoms, x+y=4, and x and y are integers greater than 1.

15. A method for forming a pattern on a processed substrate, characterized by comprising the following steps: (I-1) After applying the metal-containing film-forming composition according to claim 9 onto a substrate to be processed, a metal-containing film is formed by heat treatment, (I-2) forming a resist upper layer film on the metal-containing film using a photoresist material, (I-3) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film, (I-4) using the patterned resist upper layer film as a mask to dry-etch the transferred pattern on the metal-containing film, and (I-5) The substrate to be processed is processed 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: (II-1) Coating on the substrate to be processed After the metal-containing film-forming composition according to claim 9 is prepared, a metal-containing film is formed by heat treatment, (II-2) forming a resist intermediate film on the metal-containing film, (II-3) forming a resist upper layer film on the resist intermediate film using a photoresist material, (II-4) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film, (II-5) using the patterned resist upper layer film as a mask to dry-etch and transfer the pattern to the resist intermediate film, (II-6) using the resist intermediate film having the transferred pattern as a mask to dry-etch the transferred pattern on the metal-containing film, and (II-7) The substrate to be processed is processed using the patterned metal-containing 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: (III-1) Coating on the substrate to be processed After the metal-containing film-forming composition according to claim 9 is prepared, a metal-containing film is formed by heat treatment, (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) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film, (III-6) using the patterned resist upper layer film as a mask to dry-etch the transferred pattern on the organic thin film and the inorganic hard mask intermediate film, (III-7) using the inorganic hard mask intermediate film having the transferred pattern as a mask to dry-etch the transferred pattern on the metal-containing film, and (III-8) The substrate to be processed is processed using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

18. A method for forming a pattern on a processed substrate ， The method is characterized by having the following steps: (IV-1) Coating on the substrate to be processed After the metal-containing film-forming composition according to claim 9 is prepared, a metal-containing film is formed by heat treatment, (IV-2) forming an organic intermediate film on the metal-containing film, (IV-3) forming a combination of an inorganic hard mask interlayer film selected from a silicon-containing resist interlayer film or a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film and an organic thin film on the organic interlayer film, (IV-4) forming a resist upper layer film using a photoresist material on the silicon-containing resist intermediate film or the organic thin film, (IV-5) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film, (IV-6) using the patterned resist upper film as a mask to dry-etch the silicon-containing resist intermediate film or the organic thin film and the inorganic hard mask intermediate film to transfer the pattern, (IV-7) using the silicon-containing resist intermediate film or inorganic hard mask intermediate film to which the transferred pattern has been transferred as a mask, dry etching is performed on the organic intermediate film to transfer the pattern, (IV-8) using the organic intermediate film having the transferred pattern as a mask to dry-etch the transferred pattern on the metal-containing film, and (IV-9) The substrate to be processed is processed using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

19. A method for forming a tone reversal pattern is a method for forming a pattern on a processed substrate, characterized by comprising 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 a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film and an organic thin film on the resist underlayer film, (V-3) forming a resist upper layer film using a photoresist material on the resist intermediate film or the combination of the inorganic hard mask intermediate film and the organic thin film, (V-4) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film, (V-5) using the patterned resist upper film as a mask to dry-etch the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film to transfer the pattern, (V-6) using the resist intermediate film or the inorganic hard mask intermediate film to which the pattern has been transferred as a mask, and dry etching the transferred pattern on the resist lower layer film, (V-7) coating the patterned resist underlayer film After preparing the metal-containing film-forming composition according to claim 9, a metal-containing film is coated 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 covering the patterned resist underlayer film by chemical stripping agent or dry etching to expose the top surface of the patterned resist underlayer film, (V-9) removing the resist intermediate film or the hard mask intermediate film remaining on the top surface of the resist lower layer film by dry etching, (V-10) removing the patterned resist underlayer film exposed on the surface by dry etching to form a reverse pattern of the original pattern on the metal-containing film, (V-11) The metal-containing film having the reverse pattern formed therein is used as a mask to process the substrate to form a reverse pattern on the substrate to be processed.

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