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

Abstract

The invention relates to a compound for forming a metal-containing film, a composition for forming a metal-containing film, and a pattern forming method. The present invention addresses the problem of providing: a metal-containing film-forming compound for forming a metal-containing film that contributes to sensitivity improvement while maintaining the LWR of an upper layer resist; a metal-containing film-forming composition; and a pattern-forming method using the metal-containing film-forming composition. [Solution] A compound for forming a metal-containing film, which contains at least one metal atom (a) selected from the group consisting of Ti, Zr, and Hf, and a polydentate ligand coordinated to the metal atom (a), and wherein the polydentate ligand is substituted with a fluorine atom and has a structure represented by general formula (1) or a structure represented by general formula (2). And is derived from a compound (b) having 1-50 carbon atoms and containing one or more crosslinkable groups selected from the group consisting of a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyl group, an epoxy group, an oxetanyl group, a nitrile group, and a vinylidene group.

Description

Technical Field

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

[0002] With the high integration and high speed of LSIs, the miniaturization of pattern rules has been rapidly progressing. In particular, logic devices used in smartphones and the like have led the miniaturization and use a multiple exposure (multiple patterning lithography) process using ArF lithography, and logic devices at the 10 nm node have been mass-produced.

[0003] Next, for lithography at the 7 nm node and 5 nm node, problems such as high cost due to multiple exposures and overlay accuracy during multiple exposures have emerged, and the advent of EUV lithography that can reduce the number of exposures is expected.

[0004] Extreme ultraviolet light (EUV) with a wavelength of 13.5 nm is shorter than 1 / 10 of the wavelength of ArF excimer laser with a wavelength of 193 nm. Therefore, EUV lithography is expected to have high light contrast and high resolution. Since EUV has a short wavelength and high energy density, an acid generator is sensitive to a small number of photons. It is considered that the number of photons during EUV exposure is 1 / 14 of that during ArF exposure. In EUV exposure, the phenomenon of deterioration of line width roughness (LWR) and critical dimension uniformity (CDU) of holes due to photon deviation is regarded as a problem (Non-Patent Document 1). In addition, it has also been pointed out that there may be effects of uneven distribution, aggregation of the base polymer and acid generator, and acid diffusion from the acid generator.

[0005] As a countermeasure, for example, by lowering the post-exposure bake (PEB) temperature, LWR can be reduced, but the sensitivity of the EUV resist will be desensitized. In addition, by increasing the amount of quencher added, LWR will also be reduced, but this method will also desensitize. In order to put EUV resist into practical use, it is necessary to break the trade-off relationship between sensitivity and LWR.

[0006] Prior Art Documents

[0007] Non-Patent Documents

[0008] [Non-Patent Document 1] SPIE, Vol. 3331, p. 531 (1998) Summary of the Invention

[0009] [Problems to be Solved by the Invention]

[0010] In order to put EUV lithography into practical use as a mass production process for semiconductor devices, many problems need to be solved. Among them, the characteristics that must be improved in particular are to maintain LWR while increasing the sensitivity.

[0011] In view of the above circumstances, the present invention aims to provide a metal-containing film-forming compound for forming a metal-containing film that can contribute to the improvement of sensitivity while maintaining the LWR of the upper resist, a metal-containing film-forming composition containing the same, and a patterning method using the composition.

[0012] [Means for Solving the Problems]

[0013] In order to solve the above problems, the present invention provides a metal-containing film-forming compound,

[0014] The metal-containing film-forming compound contains at least one metal atom (a) selected from the group consisting of Ti, Zr, and Hf, and a multidentate ligand coordinated with the metal atom (a), and

[0015] The multidentate ligand is substituted with a fluorine atom and is derived from a compound (b) having 1 to 50 carbon atoms containing one or more crosslinkable groups selected from vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, oxetanyl, nitrile, and vinylene.

[0016] If it is such a metal-containing film-forming compound, a resist underlayer film or intermediate film-forming composition that can contribute to the improvement of sensitivity while maintaining the LWR of the upper resist can be obtained.

[0017] Furthermore, the compound (b) preferably contains any one of the structures represented by the following general formulas (b-1) to (b-4).

[0018] [Chemical Formula 1]

[0019]

[0020] In the above general formula, R1 to R3 are hydrogen atoms or monovalent organic groups having 1 to 30 carbon atoms which may also contain fluorine atoms, vinyl groups, allyl groups, allyloxy groups, ethynyl groups, propargyl groups, propargyloxy groups, epoxy groups, oxetanyl groups, nitrile groups, or vinylene groups; R4 to R5 are hydrogen atoms or monovalent organic groups having 1 to 30 carbon atoms which may also contain fluorine atoms, vinyl groups, allyl groups, allyloxy groups, ethynyl groups, propargyl groups, propargyloxy groups, epoxy groups, oxetanyl groups, nitrile groups, or vinylene groups; R6 to R9 are hydrogen atoms or monovalent organic groups having 1 to 30 carbon atoms which may also contain fluorine atoms, vinyl groups, allyl groups, allyloxy groups, ethynyl groups, propargyl groups, propargyloxy groups, epoxy groups, oxetanyl groups, nitrile groups, or vinylene groups; and Y is a divalent organic group having 1 to 10 carbon atoms which may also contain fluorine atoms, vinyl groups, allyl groups, allyloxy groups, ethynyl groups, propargyl groups, propargyloxy groups, epoxy groups, oxetanyl groups, nitrile groups, or vinylene groups. In the above general formula (b-2), adjacent R4 and R5 may also be bonded to each other to form an unsaturated or saturated ring structure. The compounds represented by the above general formulae (b-1) to (b-4) contain at least one fluorine atom and at least one crosslinkable group selected from vinyl groups, allyl groups, allyloxy groups, ethynyl groups, propargyl groups, propargyloxy groups, epoxy groups, oxetanyl groups, nitrile groups, and vinylene groups.

[0021] When such a metal-containing film-forming compound is used, a resist underlayer film or an intermediate film-forming composition that contributes to improving the sensitivity while maintaining the LWR of the upper resist can be obtained.

[0022] Furthermore, the compounds represented by the above general formulae (b-1) to (b-4) preferably contain at least one of an aromatic ring, a heteroaromatic ring, and an alicyclic structure.

[0023] When such a metal-containing film-forming compound is used, since it has excellent heat resistance, the amount of sublimates during the formation of a metal oxide film can be reduced, and at the same time, a large amount of a metal oxide film containing fluorine atoms can be formed.

[0024] At this time, the compounds represented by the above general formulae (b-1) to (b-4) preferably contain the structure represented by the following formula (1).

[0025] [Chemical formula 2]

[0026]

[0027] In the above formula, X m1 is a fluorine atom or a monovalent organic group having 1 to 10 carbon atoms containing a fluorine atom, and R xA monovalent organic group having 1 to 10 carbon atoms and containing one or more crosslinkable groups selected from vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, oxetanyl, nitrile, and vinylene groups, W is an organic group having 5 to 20 carbon atoms containing any one of an aromatic ring, a heteroaromatic ring, and an alicyclic structure, R A is any one selected from a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a hydroxyl group, s1 + s2 is 1 to 5, s1 is 0 to 5, s2 is 0 to 5, n2 is 0 to 2, and * is a bonding part.

[0028] If it is such a metal-containing film-forming compound, since it has excellent heat resistance, the amount of sublimates during the formation of the metal oxide film can be reduced, and at the same time, a large amount of metal oxide film containing fluorine atoms can be formed.

[0029] Furthermore, the aforementioned metal-containing film-forming compound preferably further contains a ligand (c) derived from a silicon compound represented by the following general formula (2).

[0030] [Chemical formula 3]

[0031]

[0032] In the above general formula (2), R 3A , R 3B and R 3C are each an organic group having 1 to 30 carbon atoms selected from any one of crosslinking groups represented by the following general formulas (c-1) to (c-3), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or an aryl group having 1 to 20 carbon atoms.

[0033] [Chemical formula 4]

[0034]

[0035] In the above general formulas (c-1) to (c-3), R3 is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding part.

[0036] If it is such a metal-containing film-forming compound, it will be a metal-containing film-forming compound with excellent stability, and the storage life stability of the resist underlayer film or intermediate film-forming composition can be improved.

[0037] Furthermore, the aforementioned metal-containing film-forming compound is preferably a reaction product of one or more metal-containing compounds selected from a metal compound represented by the following formula (3), and a hydrolyzate, condensate, and hydrolyzate-condensate of the metal compound represented by the following formula (3) and a compound represented by any one of the aforementioned formulas (b-1) to (b-4).

[0038] [Chemical Formula 5]

[0039] L a MX b (3)

[0040] In the formula, M is any one of Ti, Zr, and Hf. L is any one of monodentate ligands and polydentate ligands having 1 to 30 carbon atoms, and X is selected from halogen atoms, alkoxy groups, carboxylate groups, acyloxy groups, -NR a R b hydrolyzable groups. R a and R b are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. a + b = 2 to 4, and a and b are integers from 0 to 4.

[0041] By using such a metal compound, a metal-containing film with better dry etching resistance to fluorine gas and oxygen can be formed.

[0042] Furthermore, the present invention provides a composition for forming a metal-containing film, which functions as an underlayer film material or an intermediate film material for a resist used in semiconductor manufacturing, and contains:

[0043] (A) The above-mentioned compound for forming a metal-containing film, and

[0044] (B) An organic solvent.

[0045] If it is such a composition for forming a metal-containing film, an underlayer film or an intermediate film that can contribute to improving the sensitivity while maintaining the LWR of the upper resist can be formed.

[0046] Furthermore, the aforementioned composition preferably further contains one or more of (C) a crosslinking agent, (D) an acid generator, and (E) a surfactant.

[0047] If it is a composition for forming a metal-containing film containing the above additives, it will become a composition for forming a metal-containing film with better coating properties, dry etching resistance, and filling and / or planarization characteristics.

[0048] Furthermore, the aforementioned (B) organic solvent is preferably a mixture of one or more organic solvents with a boiling point below 180°C and one or more high-boiling solvents ((B') high-boiling solvents) with a boiling point of 180°C or higher.

[0049] By imparting the fluidity caused by adding the high-boiling solvent to the above-mentioned compound for forming a metal-containing film, the occurrence of coating defects caused by the drying of the composition for forming a metal-containing film can be suppressed.

[0050] Furthermore, the present invention provides a pattern forming method, which is a method for forming a pattern on a substrate to be processed, and is characterized by having the following steps:

[0051] (I-1) After coating the metal-containing film-forming composition on the substrate to be processed, heat treatment is performed to form a metal-containing film.

[0052] (I-2) An upper resist film is formed on the aforementioned metal-containing film using a photoresist material.

[0053] (I-3) After pattern exposure of the aforementioned upper resist film, development is performed with a developer to form a pattern on the aforementioned upper resist film.

[0054] (I-4) Using the upper resist film having the aforementioned pattern as a mask, the pattern is transferred to the aforementioned metal-containing film by dry etching, and

[0055] (I-5) Using the metal-containing film having the aforementioned pattern as a mask, the substrate to be processed is processed to form a pattern on the aforementioned substrate to be processed.

[0056] With the pattern formation method using the above two-layer resist process, a fine pattern can be formed on the object to be processed (substrate to be processed).

[0057] Further, the present invention provides a pattern formation method, which is a method for forming a pattern on a substrate to be processed, and is characterized by having the following steps:

[0058] (II-1) An organic lower resist film is formed on the substrate to be processed.

[0059] (II-2) After coating the metal-containing film-forming composition on the aforementioned organic lower resist film, heat treatment is performed to form a metal-containing film.

[0060] (II-3) An upper resist film is formed on the aforementioned metal-containing film using a photoresist material.

[0061] (II-4) After pattern exposure of the aforementioned upper resist film, development is performed with a developer to form a pattern on the aforementioned upper resist film.

[0062] (II-5) Using the upper resist film having the aforementioned pattern as a mask, the pattern is transferred to the aforementioned metal-containing film by dry etching.

[0063] (II-6) Using the metal-containing film having the aforementioned pattern transferred thereon as a mask, the pattern is transferred to the aforementioned organic lower resist film by dry etching, and

[0064] (II-7) Using the organic lower resist film having the aforementioned pattern as a mask, the substrate to be processed is processed to form a pattern on the aforementioned substrate to be processed.

[0065] The pattern formation method using the above three-layer resist process can form fine patterns on a workpiece with high precision.

[0066] Furthermore, the present invention provides a pattern formation method, which is a method for forming a pattern on a substrate to be processed, and is characterized by having the following steps:

[0067] (III-1) After coating the above-described metal-containing film-forming composition on the substrate to be processed and performing heat treatment, a metal-containing film is formed thereby.

[0068] (III-2) An inorganic hard mask intermediate film selected from a silicon-containing resist intermediate film, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the aforementioned metal-containing film.

[0069] (III-3) An organic thin film is formed on the aforementioned inorganic hard mask intermediate film.

[0070] (III-4) A resist upper layer film is formed on the aforementioned organic thin film using a photoresist material.

[0071] (III-5) After pattern exposure of the aforementioned resist upper layer film, development is performed with a developer, and a pattern is formed on the aforementioned resist upper layer film.

[0072] (III-6) Using the resist upper layer film having the aforementioned pattern as a mask, the pattern is transferred to the aforementioned organic thin film and the aforementioned inorganic hard mask intermediate film by dry etching.

[0073] (III-7) Using the inorganic hard mask intermediate film having the aforementioned pattern transferred thereon as a mask, the pattern is transferred to the aforementioned metal-containing film by dry etching, and

[0074] (III-8) Using the metal-containing film having the aforementioned pattern formed thereon as a mask to process the aforementioned substrate to be processed, and a pattern is formed on the aforementioned substrate to be processed.

[0075] The pattern formation method using the above four-layer resist process can form fine patterns on a workpiece with high precision.

[0076] Furthermore, the present invention provides a pattern formation method, which is a method for forming a pattern on a substrate to be processed, and is characterized by having the following steps:

[0077] (IV-1) After coating the above-described metal-containing film-forming composition on the substrate to be processed and performing heat treatment, a metal-containing film is formed thereby.

[0078] (IV-2) An organic intermediate film is formed on the aforementioned metal-containing film.

[0079] (IV-3) On the aforementioned organic intermediate film, a silicon-containing resist intermediate film or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film is formed.

[0080] (IV-4) On the aforementioned silicon-containing resist intermediate film or the aforementioned organic thin film, a resist upper layer film is formed using a photoresist material.

[0081] (IV-5) After the aforementioned resist upper layer film is pattern-exposed, it is developed with a developer, and a pattern is formed on the aforementioned resist upper layer film.

[0082] (IV-6) Using the resist upper layer film having the aforementioned pattern as a mask, the pattern is transferred to the aforementioned silicon-containing resist intermediate film or the aforementioned organic thin film and the aforementioned inorganic hard mask intermediate film by dry etching.

[0083] (IV-7) Using the silicon-containing resist intermediate film or the inorganic hard mask intermediate film having the aforementioned pattern transferred thereon as a mask, the pattern is transferred to the aforementioned organic intermediate film by dry etching.

[0084] (IV-8) Using the aforementioned organic intermediate film as a mask, the pattern is transferred to the aforementioned metal-containing film by dry etching, and

[0085] (IV-9) Using the metal-containing film having the aforementioned pattern formed thereon as a mask, the aforementioned substrate to be processed is processed, and a pattern is formed on the aforementioned substrate to be processed.

[0086] With the pattern formation method using the above multi-layer resist process, a fine pattern can be formed on the object to be processed with high precision.

[0087] Furthermore, in the aforementioned step (I-3), it is preferable to use EUV light to perform the aforementioned pattern exposure.

[0088] Furthermore, in the aforementioned step (II-4), it is preferable to use EUV light to perform the aforementioned pattern exposure.

[0089] Furthermore, in the aforementioned step (III-5), it is preferable to use EUV light to perform the aforementioned pattern exposure.

[0090] Furthermore, in the aforementioned step (IV-5), it is preferable to use EUV light to perform the aforementioned pattern exposure.

[0091] Since the compound for forming the metal-containing film of the present invention contains metal atoms with a large light absorption and fluorine atoms with a large light absorption, an anti-reflective lower layer film or intermediate film that can contribute to improving the sensitivity while maintaining the LWR of the upper resist can be formed in EUV lithography.

[0092] [Effects of the Invention]

[0093] The metal-containing film-forming compound of the present invention contains metal atoms with large light absorption and fluorine atoms with large light absorption, and thus has the characteristic that it is expected to produce a sensitizing effect by secondary electrons generated from itself during exposure in EUV lithography.

[0094] In addition, for the metal-containing film obtained in the present invention, since a high etching selectivity can be obtained with an organic material, the formed photoresist pattern can be sequentially transferred to the metal-containing film, an organic underlayer film, or a CVD organic hard mask by dry etching treatment. Especially in recent semiconductor device manufacturing processes where miniaturization has advanced, in order to prevent the collapse of the pattern after development, there is a tendency to thin the film thickness of the photoresist film, which makes it difficult to transfer the pattern to the underlayer film of the resist. However, when using the metal-containing film-forming composition of the present invention, even if a thin photoresist film is used as an etching mask, deformation of the photoresist pattern during dry etching can be suppressed, and the pattern can be transferred to the substrate with high precision. BRIEF DESCRIPTION OF THE DRAWINGS

[0095] Figure 1 (I-A) to (I-I) show the flowcharts of the pattern formation method of the present invention. DETAILED DESCRIPTION

[0096] As described above, there is a demand for the development of a metal-containing film-forming compound, a metal-containing film-forming composition containing the same, and a pattern formation method using the composition for forming an underlayer film or an intermediate film of a resist that can contribute to improving the sensitivity while maintaining the LWR of the upper resist.

[0097] As a result of repeated and in-depth studies by the present inventors to achieve the above object, it was found that by introducing fluorine atoms and crosslinkable groups into the metal-containing film-forming compound, the sensitivity can be improved without deteriorating the LWR of the upper resist, and thus the present invention was completed.

[0098] That is, the present invention is a metal-containing film-forming compound, wherein the metal-containing film-forming compound contains at least one metal atom (a) selected from the group consisting of Ti, Zr, and Hf, and a polydentate ligand coordinated with the metal atom (a), and the polydentate ligand is substituted with fluorine atoms and is a compound (b) having 1 to 50 carbon atoms containing one or more crosslinkable groups selected from vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, oxetanyl, nitrile, and vinylene.

[0099] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0100] <Metal-containing film-forming compound> ​

[0101] The metal-containing compound for film formation of the present invention contains at least one metal atom (a) selected from the group consisting of Ti, Zr, and Hf, and a multidentate ligand coordinated to the aforementioned metal atom (a), and the aforementioned multidentate ligand is substituted with a fluorine atom and is derived from a compound (b) having 1 to 50 carbon atoms containing at least one crosslinkable group selected from vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, oxetanyl, nitrile, and vinylene.

[0102] The metal-containing compound for film formation of the present invention is characterized in that the metal-containing compound for film formation comprises the following constitution.

[0103] (a) At least one metal atom selected from the group consisting of Ti, Zr, and Hf.

[0104] (b) A multidentate ligand substituted with a fluorine atom and derived from a compound (b) having 1 to 50 carbon atoms containing at least one crosslinkable group selected from vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, oxetanyl, nitrile, and vinylene.

[0105] The metal atom contained in the above metal-containing compound for film formation is at least one metal atom selected from the group consisting of Ti, Zr, and Hf. From the viewpoint of productivity, it is preferably to contain any one of Ti, Zr, and Hf. From the viewpoints of productivity and improvement of the sensitivity of the resist, it is preferably to contain any one of Ti or Hf.

[0106] The ligands coordinated in the metal-containing compound for film formation may also contain different structures, and may also contain ligands conforming to the constitution of the above (b) and general ligands other than them.

[0107] The above compound (b) is preferably any one of the structures represented by the following general formulas (b-1) to (b-4).

[0108] [Chemical formula 6]

[0109]

[0110] In the above general formula, R1 to R3 are hydrogen atoms or monovalent organic groups having 1 to 30 carbon atoms which may also contain a fluorine atom, a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyloxy group, an epoxy group, an oxetanyl group, a nitrile group, or a vinylene group; R4 to R5 are hydrogen atoms or monovalent organic groups having 1 to 30 carbon atoms which may also contain a fluorine atom, a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyloxy group, an epoxy group, an oxetanyl group, a nitrile group, or a vinylene group; R6 to R9 are hydrogen atoms or monovalent organic groups having 1 to 30 carbon atoms which may also contain a fluorine atom, a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyloxy group, an epoxy group, an oxetanyl group, a nitrile group, or a vinylene group; and Y is a divalent organic group having 1 to 10 carbon atoms which may also contain a fluorine atom, a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyloxy group, an epoxy group, an oxetanyl group, a nitrile group, or a vinylene group. In the above general formula (b-2), adjacent R4 and R5 may also bond to each other to form an unsaturated or saturated ring structure. The compounds of the above general formulas (b-1) to (b-4) contain at least one fluorine atom and at least one crosslinkable group selected from the group consisting of a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyloxy group, an epoxy group, an oxetanyl group, a nitrile group, and a vinylene group.

[0111] The metal-containing film-forming compound of the present invention contains a fluorine atom in a multidentate ligand having excellent coordination ability to a metal atom. Therefore, when it is used in a metal-containing film-forming composition, a large amount of a metal-containing film containing a fluorine atom can be formed. In addition, since a crosslinkable group is contained in the multidentate ligand, the heat resistance of the ligand containing a fluorine atom is improved. When it is used in a metal-containing film-forming composition, a larger amount of a metal-containing film containing a fluorine atom can be formed, and the sensitivity of the upper layer film of the resist can be further improved.

[0112] Furthermore, the compounds represented by the above general formulas (b-1) to (b-4) preferably contain at least one of an aromatic ring, a heteroaromatic ring, and an alicyclic structure.

[0113] The compound (b) containing a fluorine atom used as the ligand contains at least one crosslinkable group selected from the group consisting of a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyloxy group, an epoxy group, an oxetanyl group, a nitrile group, and a vinylene group. Since the heat resistance of the ligand containing a fluorine atom is further improved, when it is used in a metal-containing film-forming composition, a large amount of a metal-containing film containing a fluorine atom can be formed.

[0114] The compounds represented by the above general formulas (b-1) to (b-4) preferably contain the structure represented by the following formula (1).

[0115] [Chemical Formula 7]

[0116]

[0117] In the above formula, X m1 is a fluorine atom or a monovalent organic group having 1 to 10 carbon atoms containing a fluorine atom, and R x is a monovalent organic group having 1 to 10 carbon atoms containing one or more crosslinkable groups selected from vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, oxetanyl, nitrile, and vinylene. W is an organic group having 5 to 20 carbon atoms containing any one of an aromatic ring, a heteroaromatic ring, and an alicyclic structure. R A is any one selected from a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a hydroxyl group. s1 + s2 is 1 to 5, s1 is 0 to 5, s2 is 0 to 5, n2 is 0 to 2, and * is a bonding site.

[0118] In the above formula (1), X m1 is a fluorine atom or a monovalent organic group having 1 to 10 carbon atoms containing a fluorine atom, preferably a fluorine atom or a halogenated hydrocarbon group having 1 to 10 carbon atoms containing a fluorine atom. Specific examples of the halogenated hydrocarbon group include, for example, fluoroalkyl groups such as fluoromethyl and trifluoromethyl, and trifluoromethyl is particularly preferred.

[0119] By containing such an organic group, the resolution and sensitivity of the upper layer film of the resist can be further improved.

[0120] In the above formula (1), R A is preferably a linear alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

[0121] In the above formula (1), R x is a monovalent organic group having 1 to 10 carbon atoms containing one or more crosslinkable groups selected from vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, oxetanyl, nitrile, and vinylene. Specifically, it preferably contains a crosslinking group having the following structure.

[0122] [Chemical formula 8]

[0123]

[0124] 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 site.

[0125] [Chemical formula 9]

[0126]

[0127] In the above general formula, R bis a hydrogen atom or a methyl group, and in the same formula, they may be the same or different from each other, R c is a hydrogen atom or a saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms with or without substitution, an aryl group having 6 to 30 carbon atoms with or without substitution, or an arylalkyl group having 7 to 31 carbon atoms with or without substitution, and * represents a bonding portion.

[0128] [Chemical formula 10]

[0129]

[0130] In the formula, R e is a hydrogen atom or an organic group having 1 to 10 carbon atoms, and * represents a bonding portion.

[0131] By using a polydentate ligand having a structure in which a hydrogen atom of W in the above formula (1) is substituted with a monovalent organic group having 1 to 10 carbon atoms containing a fluorine atom or a monovalent organic group having 1 to 10 carbon atoms containing one or more crosslinkable groups selected from vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, oxetanyl, nitrile, and vinylene, the resolution and sensitivity of the upper layer film of the resist can be further improved.

[0132] In the above formula (1), W is preferably an organic group having 5 to 20 carbon atoms containing any one of an aromatic ring, a heteroaromatic ring, and an alicyclic structure, and the following structure is more preferable.

[0133] [Chemical formula 11]

[0134]

[0135] In the above formula, R is any one of the above R X 、R A 、X m1 , and * is a bonding portion.

[0136] From the viewpoint of heat resistance, in the above formula (1), it is more preferable that W contains an aromatic ring, and from the viewpoint of productivity, a benzene ring is particularly preferable.

[0137] Ideal examples of the structures represented by the above formulas (b-1) to (b-4) are listed as follows.

[0138] [Chemical formula 12]

[0139]

[0140] In the above formula, X m1And s1 is synonymous with the above formula (1), at least one or more hydrogen atoms in the above structure are substituted by a monovalent organic group having 2 to 20 carbon atoms containing at least one or more of the above crosslinkable groups, Z in the above formula is either an oxygen atom or a secondary amine, and any hydrogen atom in the above formula may also be substituted by a saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms with or without substitution, an aryl group having 6 to 30 carbon atoms with or without substitution, or an arylalkyl group having 7 to 31 carbon atoms with or without substitution.

[0141] [Chemical formula 13]

[0142]

[0143] In the above formula, X m1 And s1 is synonymous with the above formula (1), at least one or more hydrogen atoms in the above structure are substituted by a monovalent organic group having 2 to 20 carbon atoms containing at least one or more of the above crosslinkable groups, Z in the above formula is either an oxygen atom or a secondary amine, and any hydrogen atom in the above formula may also be substituted by a saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms with or without substitution, an aryl group having 6 to 30 carbon atoms with or without substitution, or an arylalkyl group having 7 to 31 carbon atoms with or without substitution.

[0144] [Chemical formula 14]

[0145]

[0146] In the above formula, X m1 And s1 is synonymous with the above formula (1), at least one or more hydrogen atoms in the above structure are substituted by a monovalent organic group having 2 to 20 carbon atoms containing at least one or more of the above crosslinkable groups, or at least one or more methylene groups in the above structure are substituted by vinylidene groups, Z in the above formula is either an oxygen atom or a secondary amine, and any hydrogen atom in the above formula may also be substituted by a saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms with or without substitution, an aryl group having 6 to 30 carbon atoms with or without substitution, or an arylalkyl group having 7 to 31 carbon atoms with or without substitution.

[0147] [Chemical formula 15]

[0148]

[0149] In the above formula, X m1And s1 is synonymous with the above formula (1). In the above formula, Y is synonymous with the above formula (b-4). At least one or more hydrogen atoms in the above structure are substituted with a monovalent organic group having 2 to 20 carbon atoms containing at least one or more of the above crosslinkable groups. Any hydrogen atom in the above formula may also be substituted with a saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms with or without substitution, an aryl group having 6 to 30 carbon atoms with or without substitution, or an arylalkyl group having 7 to 31 carbon atoms with or without substitution.

[0150] Furthermore, the metal-containing film-forming compound of the present invention is preferably a reaction product of a metal-containing compound (hereinafter referred to as (a') metal-containing compound) selected from the group consisting of a metal compound represented by the following formula (3), and a hydrolyzate, condensate, and hydrolyzate-condensate of the metal compound represented by the following formula (3) with any one of the compounds represented by the above formulas (b-1) to (b-4).

[0151] [Chemical Formula 16]

[0152] L a MX b (3)

[0153] In the formula, M is any one of Ti, Zr, and Hf. L is any one of a monodentate ligand and a polydentate ligand having 1 to 30 carbon atoms, and X is a hydrolyzable group selected from a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, and -NR a R b . R a and R b are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. a + b = 2 to 4, and a and b are integers from 0 to 4.

[0154] If such a metal-containing film-forming compound is used in a metal-containing film-forming composition, a metal-containing film excellent in dry etching resistance to fluorine gas and oxygen can be formed.

[0155] [(a') metal-containing compound]

[0156] (Hydrolyzable group)

[0157] Examples of the hydrolyzable group X in the above formula (3) include: a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, and -NR a R b . R a and R b are each preferably independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

[0158] Examples of the above halogen atom include: a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.

[0159] Examples of the above alkoxy groups include, for example: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and the like.

[0160] Examples of the above carboxylate groups include: acetate group, propionate group, butyrate group, n-hexane carboxylate group, n-octane carboxylate group, and the like.

[0161] Examples of the above acyloxy groups include, for example: acetoxy, ethenyloxy, propionyloxy, butyryloxy, tert-butyryloxy, tert-pentyryloxy, n-hexane carbonyloxy, n-octane carbonyloxy, and the like.

[0162] The above -NR a R b Examples include, for example: unsubstituted amino, methylamino, dimethylamino, diethylamino, dipropylamino, and the like.

[0163] The above hydrolyzable group X is preferably an alkoxy group, more preferably isopropoxy, n-butoxy, or tert-butoxy.

[0164] (Monodentate ligand)

[0165] Examples of the above monodentate ligand L include, for example: hydroxide ligand, carboxylate ligand, amide ligand, amine ligand, ammonia ligand, olefin ligand, and the like.

[0166] Examples of the above amide ligands include, for example: unsubstituted amide ligand (NH2), methylamide ligand (NHMe), dimethylamide ligand (NMe2), diethylamide ligand (NEt2), dipropylamide ligand (NPr2), and the like.

[0167] Examples of the above amine ligands include, for example: pyridine, trimethylamine ligand, piperidine ligand, and the like.

[0168] Examples of olefin ligands include, for example: linear olefins such as ethylene and propylene, cyclic olefins such as cyclopentene, cyclohexene, and norbornene, and the like.

[0169] (Polydentate ligand)

[0170] Examples of the above polydentate ligand L include, for example: ligands derived from hydroxy esters, ligands derived from β-diketones, ligands derived from β-keto esters, ligands derived from α,α-dicarboxylic esters, hydrocarbons with π bonds, diphosphines, and the like.

[0171] Examples of the above hydroxy esters include, for example: glycolate, lactate, 2-hydroxycyclohexane-1-carboxylate, salicylate, and the like.

[0172] Examples of the above β-diketones include, for example: acetoacetate, α-alkyl-substituted acetoacetate, β-ketovalerate, benzoylacetate, 1,3-acetonedicarboxylate, and the like.

[0173] Examples of the above α,α-dicarboxylic acid esters include, for example, malonic acid diesters, α-alkyl-substituted malonic acid diesters, α-cycloalkyl-substituted malonic acid diesters, α-aryl-substituted malonic acid diesters, and the like.

[0174] Examples of the above hydrocarbons having a π bond include, for example, chain dienes such as butadiene and isoprene, cyclic dienes such as cyclopentadiene, methylcyclopentadiene, pentamethylcyclopentadiene, cyclohexadiene, and norbornadiene, and aromatic hydrocarbons such as benzene, toluene, xylene, hexamethylbenzene, naphthalene, and indene.

[0175] Examples of the above diphosphines include, for example, 1,1-bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 2,2'-bis(diphenylphosphino)-1,1'-binaphthalene, 1,1'-bis(diphenylphosphino)ferrocene, and the like.

[0176] In the above general formula (3), a + b = 2 to 4, and a and b are integers from 0 to 4. a is preferably from 0 to 4, more preferably 2 or 4. b is preferably from 0 to 4, more preferably 0, 2, or 4. By setting a and b within the above ranges, the stability of the metal-containing film-forming compound of the present invention can be improved.

[0177] Preferred examples of the metal compound represented by formula (3) are illustrated below.

[0178] Examples of titanium-containing compounds include: titanium(IV) diisopropoxybis(2,4-pentanedionate), titanium(IV) tetra-n-butoxide, titanium(IV) tetra-n-propoxide, titanium(IV) tetraisopropoxide, titanium(IV) tri-n-butoxymonostearate, titanium(IV) butoxide oligomer, (aminopropyl)trimethoxytitanium(IV), titanium(IV) triethoxymono(2,4-pentanedionate), titanium(IV) tri-n-propoxymono(2,4-pentanedionate), titanium(IV) triisopropoxymono(2,4-pentanedionate), titanium(IV) di-n-butoxybis(2,4-pentanedionate), and the like.

[0179] Examples of zirconium-containing compounds include: zirconium(IV) dibutoxybis(ethylacetoacetate), zirconium(IV) di-n-butoxybis(2,4-pentanedionate), zirconium(IV) tetra-n-butoxide, zirconium(IV) tetra-n-propoxide, zirconium(IV) tetraisopropoxide, (aminopropyl)triethoxyzirconium(IV), (2-(3,4-epoxycyclohexyl)ethyl)trimethoxyzirconium(IV), (γ-glycidoxypropyl)trimethoxyzirconium(IV), (3-isocyanatopropyl)trimethoxyzirconium(IV), zirconium(IV) triethoxymono(2,4-pentanedionate), zirconium(IV) tri-n-propoxymono(2,4-pentanedionate), zirconium(IV) triisopropoxymono(2,4-pentanedionate), zirconium(IV) tris(3-methacryloxypropyl)methoxide, zirconium(IV) tris(3-acryloxypropyl)methoxide, and the like.

[0180] Examples of hafnium-containing compounds include: hafnium(IV) diisopropoxide bis(2,4-pentanedionate), hafnium(IV) tetrabutoxide, hafnium(IV) tetraisopropoxide, hafnium(IV) tetraethoxide, hafnium(IV) dichlorobis(cyclopentadienyl), etc.

[0181] Among these, metal alkoxides, metal formates, and metal acetates are more preferable.

[0182] When synthesizing the metal-containing film-forming compound, in addition to adding (a') the metal compound, a compound that can form a monodentate ligand or a polydentate ligand in the metal-containing film-forming compound (hereinafter referred to as (b') ligand-forming compound) can also be added.

[0183] Examples of the above (b') ligand-forming compound include organic compounds derived from hydroxyl ligands, carboxyl ligands, amide ligands, amine ligands, ammonia ligands, olefin ligands, etc. as exemplified by L in the above general formula (3); organic compounds derived from ligands from hydroxy acid esters, ligands from β-diketones, ligands from β-keto esters, ligands from α,α-dicarboxylic acid esters, etc. In addition, compounds having multiple hydroxyl groups can also be cited.

[0184] In the metal-containing film-forming compound of the present invention, the content of the ligand derived from the structure represented by the above formulas (b-1) to (b-4) should be 10 mol% to 90 mol% of the total ligands coordinated to the metal atom, more preferably 20 mol% to 80 mol%, and even more preferably 25 mol% to 75 mol%. Ligands other than the compounds represented by the above formulas (b-1) to (b-4), such as ligands from (b') the above ligand-forming compound and alkoxy groups having 1 to 10 carbon atoms, should have a content of 0 mol% to 90 mol% of the total ligands coordinated to the metal atom, and a content of 20 mol% to 80 mol% is more preferable.

[0185] In addition, when synthesizing the metal-containing film-forming compound of the present invention, in addition to adding (b') the ligand-forming compound, a (c) silicon-containing compound can also be added.

[0186] By substituting the hydrolyzable group of the (a') metal-containing compound with the (c) silicon-containing compound, the stability of the metal-containing film-forming compound of the present invention in the metal-containing film-forming composition can be improved.

[0187] Examples of the (c) silicon-containing compound include, for example, the structure represented by the following formula (2).

[0188] [Chemical formula 17]

[0189]

[0190] In the above general formula (2), R 3A, R 3B and R 3C is an organic group having 1 to 30 carbon atoms, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an aryl group having 1 to 20 carbon atoms, which is any one of the crosslinking groups represented by the following general formulas (c-1) to (c-3).

[0191] [Chemical formula 18]

[0192]

[0193] In the above general formulas (c-1) to (c-3), R3 is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding part.

[0194] The silicon-containing compound is preferably any of the compounds represented by the following formula, and from the viewpoint of productivity, trimethylsilanol is more preferable.

[0195] [Chemical formula 19]

[0196]

[0197] When the metal-containing film-forming compound of the present invention contains a ligand derived from the structure represented by the above formulas (b-1) to (b-4) and a ligand derived from the silicon-containing compound (c), in the metal-containing film-forming compound of the present invention, the content of the ligand derived from the structure represented by the above formulas (b-1) to (b-4) should be 10 mol% to 100 mol% of the total ligands coordinated with the metal atom, more preferably 20 mol% to 80 mol%, and even more preferably 25 mol% to 75 mol%. The ligand derived from the silicon-containing compound (c) should be 10 mol% to 90 mol% of the total ligands coordinated with the metal atom, more preferably 20 mol% to 80 mol%, and even more preferably 25 mol% to 75 mol%. Ligands other than the ligand-forming compound (b') and the silicon-containing compound (c), such as ligands derived from alkoxy groups having 1 to 10 carbon atoms, should be 0 mol% to 90 mol% of the total ligands coordinated with the metal atom, and more preferably 0 mol% to 75 mol%.

[0198] The synthesis method of the metal-containing compound for film formation of the present invention is not particularly limited. For example, a metal alkoxide, a metal carboxylate, or an acetylacetonate (acac) metal can be used as the (a') metal-containing compound, and it can be obtained by reacting an alkoxy group, a carboxyl group, or an acac metal with a ligand from the compounds represented by the above formulas (b-1) to (b-4). After hydrolytic condensation of the (a') metal-containing compound, it can be further reacted with a ligand from the compounds represented by the above formulas (b-1) to (b-4), or the (a') metal-containing compound can be reacted with a ligand from the compounds represented by the above formulas (b-1) to (b-4) and then hydrolytically condensed. When it is difficult to control the hydrolytic condensation, the reaction can also be carried out with a ligand from the compounds represented by the above formulas (b-1) to (b-4) in a non-aqueous environment. They should be appropriately adjusted according to the necessary characteristics of the metal-containing compound for film formation and the metal-containing film of the present invention. When there are a (c) silicon-containing compound and the compounds represented by the above formulas (b-1) to (b-4) as ligands, it is advisable to react the (a') metal-containing compound with the (c) silicon-containing compound and then react with a ligand from the compounds represented by the above formulas (b-1) to (b-4).

[0199] Examples of the method for carrying out the hydrolytic condensation reaction using the (a') metal-containing compound include: a method of carrying out the hydrolytic condensation reaction of the (a') metal-containing compound in a solvent containing water, etc. At this time, other compounds having a hydrolyzable group can also be added as needed. Also, an acid such as acetic acid can be added as a catalyst for the hydrolytic condensation reaction. Regarding the lower limit of the amount of water used in this hydrolytic condensation reaction, it should be 0.2 times the molar amount, more preferably 1 times the molar amount, and even more preferably 3 times the molar amount, relative to the hydrolyzable group contained in the (a') metal-containing compound, etc. The upper limit of the above amount of water should be 20 times the molar amount, more preferably 15 times the molar amount, and even more preferably 10 times the molar amount.

[0200] The solvent used in the synthesis reaction of the metal-containing film-forming compound of the present invention is not particularly limited. For example, the same solvents as those exemplified later as (B) organic solvents can be used. Representative solvents and solvent mixtures include those containing ester, ether, or alcohol functional groups. For example, a mixture of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) in a volume ratio of 70 / 30. Examples of other solvents that can be used include: butanediol 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, isoamyl 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 monoter-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, etc.

[0201] <Metal-containing film-forming composition>

[0202] Furthermore, the present invention provides a metal-containing film-forming composition that functions as an underlayer film material or an intermediate film material for a resist used in semiconductor manufacturing, and contains: (A) the above-mentioned metal-containing film-forming compound, and (B) an organic solvent.

[0203] <(A) Metal-containing film-forming compound>

[0204] (A) The metal-containing film-forming compound uses the above-mentioned metal-containing film-forming compound of the present invention. In the composition, the blending amount of component (A) is not particularly limited. For example, it can be 1 to 20 parts by mass, preferably 2 to 10 parts by mass, relative to the total of 100 parts by mass of components (A) and (B).

[0205] <(B) Organic solvent>

[0206] The (B) organic solvent that can be used in the metal-containing film-forming composition of the present invention is not particularly limited as long as it can dissolve or disperse the above-mentioned (A) metal-containing film-forming compound, and can dissolve or disperse the following (C) crosslinking agent, (D) acid generator, (E) surfactant, (B') high-boiling solvent, and other additives when contained.

[0207] Specifically, for example, an organic solvent described in paragraphs

[0091] to

[0092] of Japanese Patent 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 them may preferably be used.

[0208] The blending amount of the organic solvent is preferably 200 to 10,000 parts, more preferably 250 to 5,000 parts, relative to 100 parts by mass of the metal-containing film-forming compound (A).

[0209] <(B’) High-boiling solvent>

[0210] In the metal-containing film-forming composition of the present invention, the aforementioned (B) organic solvent may also contain a (B’) high-boiling solvent. The (B’) high-boiling solvent may be one or more organic solvents having a boiling point of 180 degrees Celsius (°C) or higher.

[0211] For example, as the (B) organic solvent, 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’) high-boiling solvent) may also be used.

[0212] (B’) If the high-boiling solvent can dissolve each component in the metal-containing film-forming composition of the present invention, there are no particular restrictions on hydrocarbons, alcohols, ketones, esters, ethers, chlorinated solvents, etc. Specific examples can be exemplified as follows: 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, n-nonyl acetate, monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl 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 monon-propyl ether, dipropylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monon-propyl ether, tripropylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol methyl n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-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. They can be used alone or in combination.

[0213] (B’) The blending amount of the high-boiling solvent, such as the temperature for heat-treating the metal-containing film-forming composition of the present invention, can be appropriately selected from the above. The boiling point of the high-boiling solvent is preferably 180°C to 300°C, more preferably 200°C to 300°C. If the boiling point is such, there is no concern that the volatilization during baking (heat treatment) becomes too fast, so the occurrence of defects caused by drying during film formation can be suppressed. Also, if the boiling point is such, there is no situation where it remains unvolatile after baking and remains in the film, so there is no concern about adversely affecting the film physical properties such as etching resistance.

[0214] Furthermore, the blending amount when using the (B’) high-boiling solvent, relative to 100 parts by mass of the organic solvent with a boiling point below 180°C, is preferably set to 1 to 30 parts by mass. If the blending amount is such, sufficient thermal fluidity can be imparted during baking, and it will not remain in the film and is irrelevant to the deterioration of film physical properties such as etching resistance, so it is more ideal.

[0215] <Other components>

[0216] The above-described metal-containing film-forming composition can be used as a resist underlayer film or an intermediate film used in a multilayer resist process. It suffices if it contains one or more of the above-mentioned (A) metal-containing film-forming compounds and (B) organic solvents, and may also contain at least one of (C) crosslinking agents, (D) acid generators, (E) surfactants, and (B') high-boiling solvents as needed.

[0217] Hereinafter, components other than the above-mentioned (A) metal-containing film-forming compounds and (B) organic solvents that can be contained in the metal-containing film-forming composition of the present invention will be described.

[0218] [(C) Crosslinking agent]

[0219] Furthermore, in the metal-containing film-forming composition of the present invention, a (C) crosslinking agent may be added in order to improve the curability and further suppress the mutual mixing with the resist upper layer film.

[0220] The crosslinking agent is not particularly limited, and various known crosslinking agents can be widely used. Examples thereof include: melamine-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.

[0221] The above-mentioned (C) crosslinking agent can be used alone or in combination of two or more. When adding the crosslinking agent, the addition amount is preferably 5 to 50 parts, more preferably 10 to 40 parts, relative to 100 parts of the above-mentioned (A) metal-containing film-forming compound. If the addition amount is 5 parts or more, sufficient curability can be exhibited, and the mutual mixing with the resist upper layer film can be suppressed. On the other hand, if the addition amount is 50 parts or less, there is no concern about the deterioration of dry etching resistance due to the decrease in the ratio of the (A) metal-containing film-forming compound in the composition.

[0222] Specific examples of melamine-based crosslinking agents include: hexamethoxymethylated melamine, hexabutoxymethylated melamine, their alkoxy and / or hydroxy substituents, and their partial self-condensates.

[0223] Specific examples of glycoluril-based crosslinking agents include: tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, their alkoxy and / or hydroxy substituents, and their partial self-condensates.

[0224] Specific examples of the benzoguanamine-based crosslinking agent include: tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, their alkoxy and / or hydroxy substituents, and their partial self-condensates.

[0225] Specific examples of the urea-based crosslinking agent include: dimethoxymethylated dimethoxyethyleneurea, its alkoxy and / or hydroxy substituents, and their partial self-condensates.

[0226] Specific examples of the β-hydroxyalkylamide-based crosslinking agent include: N,N,N’,N’-tetrakis(2-hydroxyethyl)adipamide.

[0227] Specific examples of the isocyanurate-based crosslinking agent include: triglycidyl isocyanurate, triallyl isocyanurate.

[0228] Specific examples of the aziridine-based crosslinking agent include: 4,4’-bis(ethyleneiminocarbonylamino)diphenylmethane, 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate].

[0229] Specific examples of the oxazoline-based crosslinking agent include: 2,2’-isopropylidenebis(4-benzyl-2-oxazoline), 2,2’-isopropylidenebis(4-phenyl-2-oxazoline), 2,2’-methylenebis4,5-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), 2-isopropenyl oxazoline copolymer.

[0230] Specific examples of the epoxy-based 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, pentaerythritol tetraglycidyl ether.

[0231] Specific examples of the phenol-based crosslinking agent include: the compound represented by the following general formula (10).

[0232] [Chemical formula 20]

[0233]

[0234] In the formula, Q is a single bond or a q-valent hydrocarbon group having 1 to 20 carbon atoms. R 1 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. q 16 is an integer of 1 to 5. 1

[0235] Q is a single bond or a q-valent hydrocarbon group having 1 to 20 carbon atoms. q 1 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. q1 is an integer of 1 to 5, more preferably 2 or 3. Q can be specifically exemplified as: methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, eicosane. R 16 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms can be specifically exemplified as: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, ethylhexyl, decyl, eicosyl, and is preferably a hydrogen atom or a methyl group.

[0236] Examples of the compound represented by the above general formula (10) can be specifically exemplified as the following compounds. Among them, from the viewpoints of improving the hardening property and film thickness uniformity of the conformal film, it is preferably the hexa-methoxymethylated product of triphenylmethane, triphenylethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and 1-ethyl-4-isopropylbenzene tris(4-hydroxyphenyl).

[0237] [Chemical formula 21]

[0238]

[0239] [Chemical formula 22]

[0240]

[0241] <(D) Acid generator>

[0242] In the metal-containing film-forming composition of the present invention, in order to further promote the hardening reaction of the above-mentioned (A) metal-containing film-forming compound, a (D) acid generator can be added. The acid generator is one that generates an acid by thermal decomposition or one that generates an acid by irradiation, and either one can be added. Specifically, the materials described in paragraphs

[0061] to

[0085] of Japanese Patent Application Laid-Open No. 2007-199653 can be added, but it is not limited thereto.

[0243] The above acid generator can be used alone or in combination of two or more. When adding the acid generator, the addition amount is preferably 0.05 to 50 parts, more preferably 0.1 to 10 parts, based on 100 parts by mass of the above-mentioned (A) metal-containing film-forming compound.

[0244] <(E) Surfactant>

[0245] In the metal-containing film-forming composition of the present invention, in order to improve coatability during spin coating, (E) a surfactant may be added. As the surfactant, for example, those described in paragraphs

[0142] to

[0147] of Japanese Patent Application Laid-Open No. 2009-269953 can be used. When adding the surfactant, the addition amount is preferably 0.01 to 10 parts, more preferably 0.05 to 5 parts, relative to 100 parts by mass of the above-mentioned (A) metal-containing film-forming compound.

[0246] <Metal-containing film-forming method>

[0247] The present invention provides a method of using the above-mentioned metal-containing film-forming composition to form a filling film that functions as an underlayer resist film, an intermediate film for a multilayer resist film used in lithography, or a planarization film for semiconductor manufacturing.

[0248] In the metal-containing film-forming method using the metal-containing film-forming composition of the present invention, the above-mentioned metal-containing film-forming composition is coated on a substrate to be processed by a spin coating method or the like. By using a spin coating method or the like, good filling characteristics can be obtained. After spin coating, baking (heat treatment) is performed to evaporate the solvent, prevent mixing with the upper resist film and the intermediate resist film, and promote the crosslinking reaction. The baking is preferably performed in the range of 100°C or higher and 600°C or lower, for 10 to 600 seconds, and more preferably in the range of 200°C or higher and 500°C or lower, for 10 to 300 seconds. Considering the influence on device damage and wafer deformation, the upper limit of the heating temperature in the wafer process for lithography is preferably set to 600°C or lower, and more preferably 500°C or lower.

[0249] Furthermore, in the metal-containing film-forming method using the metal-containing film-forming composition of the present invention, by coating the metal-containing film-forming composition of the present invention on a substrate to be processed by the same spin coating method or the like and calcining the metal-containing film-forming composition in an environment with an oxygen concentration of 0.1% by volume or higher and 21% by volume or lower, a metal-containing film can also be formed.

[0250] By calcining the metal-containing film-forming composition of the present invention in such an oxygen environment, a sufficiently hardened film can be obtained. The environment during baking may be air, but it is more ideal to previously enclose an inert gas such as N2, Ar, or He to reduce oxygen in order to prevent oxidation of the metal-containing film. In order to prevent oxidation, it is necessary to control the oxygen concentration, which is preferably 1000 ppm or lower, and more preferably 100 ppm or lower (volume basis). Preventing oxidation of the metal-containing film during baking is more ideal because there will be no increase in absorption or reduction in etching resistance.

[0251] <Pattern formation method using a metal-containing film-forming composition>

[0252] Next, a method for forming a pattern using the metal-containing film-forming composition of the present invention will be described.

[0253] <Two-layer resist process>

[0254] The present invention provides a pattern-forming method for a two-layer resist process using the above-mentioned metal-containing film-forming composition, which has the following steps:

[0255] (I-1) After coating the above-mentioned metal-containing film-forming composition on the substrate to be processed, heat treatment is performed to form a metal-containing film.

[0256] (I-2) An upper resist film is formed on the aforementioned metal-containing film using a photoresist material.

[0257] (I-3) After the aforementioned upper resist film is pattern-exposed, it is developed with a developer to form a pattern on the aforementioned upper resist film.

[0258] (I-4) Using the upper resist film with the aforementioned pattern as a mask, and transferring the pattern to the aforementioned metal-containing film by dry etching, and

[0259] (I-5) Using the metal-containing film with the aforementioned pattern as a mask to process the aforementioned substrate to be processed, and forming a pattern on the aforementioned substrate to be processed.

[0260] The upper resist film of the above two-layer resist process exhibits etching resistance to chlorine-based gases. Therefore, in the above two-layer resist process, for the dry etching of the metal-containing film performed using the upper resist film as a mask, it is advisable to use an etching gas mainly composed of chlorine-based gas.

[0261] In order to ensure the adhesion to the upper resist film, an adhesion film can also be formed between the upper resist film and the metal-containing film of the present invention. The adhesion film can be an organic film or a silicon-containing film containing polysiloxane.

[0262] The pattern-forming method of the present invention for the resist process using the above-mentioned metal-containing film-forming composition helps to improve the exposure sensitivity of the upper resist film. Therefore, it is advisable to use it as a lower layer film close to the upper resist film, and it is better to use it immediately below the upper resist film. When an adhesion film is used between the upper resist film and the metal-containing film, the film thickness of the adhesion film should be 20 nm or less, more preferably 15 nm or less, and even more preferably 10 nm or less. The thinner the film thickness of the adhesion film, the greater the proportion of the contribution of the metal-containing film to the improvement of the exposure sensitivity of the upper resist film, which is more ideal.

[0263] <Three-layer resist process>

[0264] Furthermore, regarding a pattern formation method for a three-layer resist process using such a metal-containing film-forming composition, the present invention provides a pattern formation method characterized by the following steps:

[0265] (II-1) Form an organic resist lower layer film on the substrate to be processed.

[0266] (II-2) After coating the above metal-containing film-forming composition on the organic resist lower layer film, perform heat treatment to form a metal-containing film.

[0267] (II-3) Form a resist upper layer film on the above metal-containing film using a photoresist material.

[0268] (II-4) After pattern-exposing the above resist upper layer film, develop it with a developer to form a pattern on the above resist upper layer film.

[0269] (II-5) Use the resist upper layer film with the above pattern formed thereon as a mask, and transfer the pattern to the above metal-containing film by dry etching.

[0270] (II-6) Use the metal-containing film with the above pattern transferred thereon as a mask, and transfer the pattern to the above organic resist lower layer film by dry etching, and

[0271] (II-7) Use the organic resist lower layer film with the above pattern formed thereon as a mask to process the above substrate to be processed, and form a pattern on the above substrate to be processed.

[0272] Regarding the pattern formation method for the three-layer resist process of the present invention, an explanation will be given with reference to Figure 1 First, after forming an organic resist lower layer film 2 (I-A) on the substrate to be processed 1, a metal-containing film 3 (I-B) serving as a resist intermediate film is formed using the metal-containing film-forming composition of the present invention, and a resist upper layer film 4 (I-C) is formed thereon using a photoresist material. Then, the resist upper layer film 4 is exposed P (I-D) using a mask 5, and PEB (post-exposure bake) is performed (I-E). Then, development is performed to form a resist upper layer film pattern 4a (I-F). Then, using the resist upper layer film pattern 4a as a mask, the metal-containing film 3 is dry-etched to form a metal-containing film pattern 3a (I-G). Then, after removing the resist upper layer film pattern 4a, using the metal-containing film pattern 3a as a mask, the organic resist lower layer film 2 is dry-etched to form an organic resist lower layer film pattern 2a (I-H). Further, after removing the metal-containing film pattern 3a, using the organic resist lower layer film pattern 2a as a mask, the substrate to be processed 1 is etched to form a pattern 1a (I-I).

[0273] The metal-containing film in the above three-layer resist process exhibits etching resistance to oxygen-based gases. Therefore, in the above three-layer resist process, for the dry etching of the organic resist lower layer film using the metal-containing film as a mask, it is advisable to use an etching gas with an oxygen-based gas as the main component.

[0274] Regarding the organic resist lower layer film material that can be used for the above organic resist lower layer film, those that are publicly known as the lower layer film for the three-layer resist method or the two-layer resist method using a silicon resist composition can be used. In addition to the novolak resin (molecular weight 11,000) of 4,4'-(9-fluorenylidene) bisphenol described in Japanese Patent Application Laid-Open No. 2005-128509, various resins represented by novolak resins and those publicly known as the resist lower layer film materials for the two-layer resist method and the three-layer resist method can also be used. Also, when it is desired to further improve the heat resistance compared to ordinary novolak resins, a polycyclic skeleton such as 6,6'-(9-fluorenylidene)-bis(2-naphthol) novolak resin can be added, and a polyimide-based resin (for example, Japanese Patent Application Laid-Open No. 2004-153125) can also be selected.

[0275] The above organic resist lower layer film can use a composition solution and be formed on the substrate to be processed by a spin coating method or the like in the same manner as the photoresist composition. After forming the organic resist lower layer film by a spin coating method or the like, baking is advisable to evaporate the organic solvent. The baking temperature can ideally be in the range of 80 to 400 °C, and the baking time can ideally be in the range of 10 to 300 seconds.

[0276] The above organic resist lower layer film material can also be replaced with an organic hard mask formed by CVD method or ALD method.

[0277] Furthermore, the present invention can also set the pattern formation method of the three-layer resist process using the composition for forming the metal-containing film as a pattern formation method characterized as follows: forming a metal-containing film on the substrate to be processed using the composition for forming the metal-containing film, forming an inorganic hard mask intermediate film selected from a silicon-containing resist intermediate film, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film, then forming a resist upper layer film on the inorganic hard mask using a photoresist material, performing pattern exposure on the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film, using the patterned resist upper layer film as a mask, transferring the pattern to the inorganic hard mask intermediate film by dry etching, using the inorganic hard mask intermediate film with the transferred pattern as a mask, transferring the pattern to the metal-containing film by dry etching, and then processing the substrate to be processed using the metal-containing film with the formed pattern as a mask to form a pattern on the substrate to be processed.

[0278] <Four-layer resist process>

[0279] In addition, regarding the pattern formation method for a four-layer resist process using such a metal-containing film-forming composition, the present invention provides a pattern formation method, which is characterized by having the following steps:

[0280] (III-1) After coating the above-mentioned metal-containing film-forming composition on the substrate to be processed, heat treatment is performed to thereby form a metal-containing film.

[0281] (III-2) An inorganic hard mask intermediate film selected from a silicon-containing resist intermediate film, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the aforementioned metal-containing film.

[0282] (III-3) An organic thin film (such as an organic antireflection film (BARC) or a bonding film) is formed on the aforementioned inorganic hard mask intermediate film.

[0283] (III-4) A resist upper layer film is formed on the aforementioned organic thin film using a photoresist material.

[0284] (III-5) After pattern exposure of the aforementioned resist upper layer film, development is performed with a developer to form a pattern on the aforementioned resist upper layer film.

[0285] (III-6) Using the resist upper layer film having the aforementioned pattern as a mask, the pattern is transferred to the aforementioned organic thin film and the aforementioned inorganic hard mask intermediate film by dry etching.

[0286] (III-7) Using the inorganic hard mask intermediate film having the aforementioned pattern transferred thereto as a mask, the pattern is transferred to the aforementioned metal-containing film by dry etching, and

[0287] (III-8) Using the metal-containing film having the aforementioned pattern formed thereon as a mask, the aforementioned substrate to be processed is processed to form a pattern on the aforementioned substrate to be processed.

[0288] At this time, the aforementioned inorganic hard mask intermediate film is preferably formed by a CVD method or an ALD method.

[0289] If the above-mentioned inorganic hard mask is formed by a CVD method or an ALD method, fine patterns can be formed on the object to be processed with higher precision.

[0290] When a silicon-containing resist interlayer is used as the inorganic hard mask interlayer in the above-described pattern forming method, a polysiloxane-based interlayer can also be desirably used as the silicon-containing resist interlayer. By providing the silicon-containing resist interlayer with an antireflection effect, reflection can be suppressed. In particular, for 193 nm exposure, if a material containing a large amount of aromatic groups and having a high etching selectivity with respect to the substrate is used for the organic film, the k value becomes high and the substrate reflection becomes high. However, for the silicon-containing resist interlayer, reflection can be suppressed by providing it with an absorption that gives an appropriate k value, and the substrate reflection can be set to 0.5% or less. For the silicon-containing resist interlayer having an antireflection effect, a polysiloxane having a pendant anthracenyl group and crosslinked by an acid or heat can be desirably used for 248 nm and 157 nm exposure, and a polysiloxane having a pendant phenyl group or a light-absorbing group having a silicon-silicon bond and crosslinked by an acid or heat can be desirably used for 193 nm exposure.

[0291] An inorganic hard mask can also be formed as the inorganic hard mask interlayer. In this case, at least on the workpiece, a metal-containing film is formed using the metal-containing film-forming composition of the present invention, and an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the metal-containing film. Then, a resist upper layer film is formed on the inorganic hard mask using a photoresist composition, and a circuit pattern is formed in the resist upper layer film. Then, the inorganic hard mask is etched using the resist upper layer film having the pattern as a mask, the metal-containing film is etched using the inorganic hard mask having the pattern as a mask, and the workpiece is etched using the metal-containing film having the pattern as a mask, and a pattern is formed on the workpiece. Thus, a semiconductor device circuit pattern can be formed on the substrate.

[0292] As described above, when an inorganic hard mask is formed on the metal-containing film, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film (SiON film) can be formed by a CVD method, an ALD method, or the like. For example, a method for forming a silicon nitride film is described in Japanese Patent Application Laid-Open No. 2002-334869 and International Publication No. 2004 / 066377. The film thickness of the inorganic hard mask is preferably 5 to 200 nm, more preferably 10 to 100 nm. Further, the inorganic hard mask can most desirably use a SiON film having a high antireflection film effect. Since the substrate temperature during the formation of the SiON film reaches 300 to 500°C, the metal-containing film needs to withstand a temperature of 300 to 500°C. The metal-containing film-forming composition used in the present invention has high heat resistance and can withstand a high temperature of 300°C to 500°C. Therefore, an inorganic hard mask formed by a CVD method or an ALD method and a metal-containing film formed by a spin coating method can be combined.

[0293] As described above, a photoresist film may be formed on the inorganic hard mask as the upper resist film. However, an organic antireflective coating (BARC) or a conformal film may also be spin-coated on the inorganic hard mask, and a photoresist film may be formed thereon. In particular, when a SiON film is used as the inorganic hard mask, reflection can be suppressed even in immersion exposure with a high NA exceeding 1.0 caused by the two-layer antireflective films of the SiON film and the BARC. Another advantage of forming the BARC is that it has the effect of reducing the tailing of the photoresist pattern immediately above the SiON film.

[0294] In the above-described pattern formation method, the upper resist film may be positive or negative, and the same photoresist composition as that commonly used can be used. Further, 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 forming the upper resist film from the above-described photoresist composition, it may be a method of forming by spin coating or a vapor deposition process such as CVD or ALD.

[0295] When forming the photoresist composition by spin coating, prebaking is performed after resist coating, preferably in the range of 60 to 180°C for 10 to 300 seconds. Thereafter, exposure is performed according to a common method, and post-exposure baking (PEB) and development are performed to obtain a resist pattern. In addition, the thickness of the upper resist film is not particularly limited, preferably 10 to 500 nm, and particularly preferably 20 to 400 nm.

[0296] When forming the photoresist composition by a vapor deposition process such as CVD or ALD, the above-described resist composition is an EUV-sensitive metal oxide film, and the above-described metal is selected from Sn, Zr, Hf, Ti, Bi, Sb, etc., and preferably Sn with excellent EUV sensitivity. The metal oxide-containing film may be a photosensitive organometallic oxide film such as an organotin oxide (e.g., haloalkyl Sn, alkoxyalkyl Sn, or amidoalkyl Sn). Specific examples of suitable precursors include trimethyltin chloride, dimethylditin dichloride, chloroformtin, tris(dimethylamino)methyltin(IV), and (dimethylamino)trimethyltin(IV).

[0297] For the metal oxide film, for example, a Lam Vector (registered trademark) tool can be used, and evaporation coating can be performed by PECVD or PEALD. In the ALD example, the Sn oxide precursor is separated from the O precursor / plasma. The evaporation coating temperature should preferably be in the range of 50°C to 600°C. The evaporation coating pressure should preferably be between 100 and 6000 mTorr. The flow rate of the precursor liquid of the film containing metal oxide (such as an organic tin oxide precursor) can be 0.01 to 10 cmm, and the gas flow rate (CO2, CO, Ar, N2) can be 100 to 10000 sccm. High-frequency plasma (such as 13.56 MHz, 27.1 MHz, or a frequency higher than these) is used for the plasma power, and 200 to 1000 W is sufficient for each 300 mm wafer station.

[0298] The evaporation coating thickness should preferably be

[0299] The exposure light can include high-energy rays with a wavelength of 300 nm or less. Specifically, it can include: excimer lasers of 248 nm, 193 nm, 157 nm, soft X-rays of 3 to 20 nm, electron beams, X-rays, etc.

[0300] The above method for forming a pattern on the upper resist film can be used for pattern formation by optical lithography with a wavelength of 5 nm or more and 300 nm or less, electron beam direct writing, nanoimprinting, or a combination thereof, but EUV light is optimal in the present invention.

[0301] Also, the developing method in the aforementioned pattern forming method should preferably be alkali development or development with an organic solvent.

[0302] Then, etching is performed using the obtained resist pattern as a mask. For the etching of the silicon-containing resist intermediate film and the inorganic hard mask in the three-layer resist process, a freon-based gas is used and the upper resist pattern is used as a mask. Thereby, a silicon-containing resist intermediate film pattern and an inorganic hard mask pattern are formed.

[0303] Then, using the obtained silicon-containing resist intermediate film pattern and inorganic hard mask pattern as masks, etching processing of the metal-containing film is performed. The etching processing of the metal-containing film should preferably be performed using an etching gas mainly composed of a chlorine-based gas.

[0304] The etching of the next workpiece to be processed can also be performed using a conventional method. For example, if the workpiece to be processed is SiO2, SiN, or a silicon dioxide-based low dielectric constant insulating film, etching is performed using a freon-based gas as the main component. When the substrate is etched with a freon-based gas, the silicon-containing resist intermediate film pattern in the three-layer resist process will be peeled off simultaneously with the substrate processing.

[0305] The metal-containing film obtained using the metal-containing film-forming composition of the present invention is characterized by excellent etching resistance during etching of these workpieces.

[0306] In addition, the workpiece (workpiece substrate) is not particularly limited, and substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc., or those with a processed layer formed on the substrate can be used. For the processed layer, various Low-k films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, etc., and their barrier films can be used. Generally, a thickness of 50 to 10,000 nm can be formed, and particularly a thickness of 100 to 5,000 nm can be formed. In addition, when forming the processed layer, different materials can be used for the substrate and the processed layer.

[0307] <Multi-layer resist process>

[0308] Furthermore, the present invention provides a pattern formation method for a multi-layer resist process using such a metal-containing film-forming composition, which is characterized by having the following steps:

[0309] (IV-1) After coating the above-mentioned metal-containing film-forming composition on the workpiece substrate, heat treatment is performed to form a metal-containing film.

[0310] (IV-2) An organic intermediate film is formed on the aforementioned metal-containing film.

[0311] (IV-3) A silicon-containing resist intermediate film or a combination of an inorganic hard mask intermediate film selected from silicon oxide films, silicon nitride films, and silicon oxynitride films and an organic thin film is formed on the aforementioned organic intermediate film.

[0312] (IV-4) A resist upper layer film is formed on the aforementioned silicon-containing resist intermediate film or the aforementioned organic thin film using a photoresist material.

[0313] (IV-5) After pattern exposure of the aforementioned resist upper layer film, development is performed with a developer to form a pattern on the aforementioned resist upper layer film.

[0314] (IV-6) Using the resist upper layer film with the aforementioned pattern formed as a mask, the pattern is transferred to the aforementioned silicon-containing resist intermediate film or the aforementioned organic thin film and the aforementioned inorganic hard mask intermediate film by dry etching.

[0315] (IV-7) Using the silicon-containing resist intermediate film or the inorganic hard mask intermediate film with the aforementioned pattern transferred as a mask, the pattern is transferred to the aforementioned organic intermediate film by dry etching.

[0316] (IV-8) Using the aforementioned organic intermediate film as a mask, and transferring the pattern to the aforementioned metal-containing film by dry etching, and

[0317] (IV-9) Using the metal-containing film with the aforementioned pattern formed thereon as a mask to process the aforementioned substrate to be processed, and forming a pattern on the aforementioned substrate to be processed.

[0318] As an example of a pattern formation method for a multilayer resist process using a composition for forming such a metal-containing film, a pattern formation method characterized by the following steps can be cited: forming a metal-containing film on the substrate to be processed using the aforementioned composition for forming a metal-containing film, forming an organic intermediate film on the metal-containing film using an organic resist underlayer film material, forming a silicon-containing resist intermediate film on the organic intermediate film using a silicon-containing resist intermediate film material, and forming an organic anti-reflective coating (BARC) or a sealing film on the silicon-containing resist intermediate film as needed, then forming a resist upper layer film on the silicon-containing resist intermediate film or the BARC or the sealing film using a photoresist material, performing pattern exposure on the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film, using the resist upper layer film with the pattern formed thereon as a mask, transferring the pattern to the BARC or the sealing film and the silicon-containing resist intermediate film by dry etching, using the silicon-containing resist intermediate film with the pattern transferred thereon as a mask, transferring the pattern to the organic intermediate film by dry etching, then using the organic intermediate film as a mask to transfer the pattern to the metal-containing film, and using the metal-containing film with the pattern formed thereon as a mask to process the substrate to be processed, and forming a pattern on the substrate to be processed.

[0319] Regarding the organic resist underlayer film material that can be used for the aforementioned organic intermediate film, those that are publicly known as the underlayer film for the three-layer resist method or the two-layer resist method using a silicon resist composition can be used. In addition to 4,4'-(9-fluorenylidene) bisphenol novolak resin (molecular weight 11,000) described in Japanese Patent Application Laid-Open No. 2005-128509, various resins represented by novolak resin and publicly known as the resist underlayer film material for the two-layer resist method and the three-layer resist method can also be used. Also, when it is desired to further improve the heat resistance compared to ordinary novolak resin, a polycyclic skeleton such as 6,6'-(9-fluorenylidene)-bis(2-naphthol) novolak resin can be added, and a polyimide-based resin (for example, Japanese Patent Application Laid-Open No. 2004-153125) can also be selected.

[0320] The above-mentioned organic intermediate film can use a composition solution and can be formed on a substrate to be processed by a spin coating method or the like in the same manner as a photoresist composition. After forming the organic lower layer film by a spin coating method or the like, baking is preferably performed to evaporate the organic solvent. The baking temperature can ideally be in the range of 80 to 400 °C, and the baking time can ideally be in the range of 10 to 300 seconds.

[0321] The above-mentioned organic resist lower layer film material can also be replaced with an organic hard mask formed by CVD method or ALD method.

[0322] The organic intermediate film in the above multi-layer resist process exhibits etching resistance against chlorine-based gases. Therefore, in the above multi-layer resist process, for the dry etching of a metal-containing film using the organic intermediate film as a mask, an etching gas mainly composed of chlorine-based gas is preferably used.

[0323] Examples

[0324] The following synthesis examples, examples, and comparative examples illustrate the present invention more specifically, but the present invention is not limited by them.

[0325] [Synthesis of Compounds (A-1) to (A-13) for Forming Metal-Containing Films]

[0326] In the following synthesis examples, the following organic group raw material groups G: (G1) to (G8) and silicon-containing organic group raw material groups H: (H1) to (H2) are used.

[0327] Raw material group G: (G1) to (G8) are as follows.

[0328] [Chemical formula 23]

[0329]

[0330] Raw material group H: (H1) to (H2) are as follows.

[0331] [Chemical formula 24]

[0332]

[0333] The metal source M uses the following metal compounds.

[0334] (M1): Hafnium(IV) n-butoxide

[0335] (M2): Titanium tetraisopropoxide

[0336] (M3): Zirconium(IV) tetrabutoxide (80 wt% 1-butanol solution)

[0337] [Synthesis Example 1] Synthesis of Compound (A-1) for Forming Metal-Containing Film

[0338] Under a nitrogen atmosphere, 23.5 g of hafnium(IV) butoxide (M1) was dissolved in 25.5 g of a PGMEA / PGME (weight ratio 70 / 30) solution. While stirring, the reaction temperature was set to 60°C and stirring was continued for 2 hours. Then, a mixture obtained by suspending 19.6 g of compound G1 in 22.0 g of a PGMEA / PGME (weight ratio 70 / 30) solution was added to the aforementioned reaction system, and the reaction temperature was maintained at 60°C while stirring for 1 hour. After cooling to room temperature, the resulting reaction solution was filtered through a 0.45-μm PTFE filter to obtain a PGMEA / PGME solution of the metal-containing film-forming compound (A-1). The concentration of the components other than the solvent in this solution was 23% by mass.

[0339] [Synthesis Examples 2 to 10] Synthesis of Compounds (A-2) to (A-9) and Comparative Example Compound (R-1)

[0340] Using the above metal source M and the above compound group G in the feed amounts shown in Table 1, the compounds (A-2) to (A-9) and the comparative example compound (R-1) shown in Table 1 were obtained under the same reaction conditions as in Synthesis Example 1.

[0341] [Table 1]

[0342]

[0343] [Synthesis Example 11] Synthesis of Metal-Containing Film-Forming Compound (A-10)

[0344] Under a nitrogen atmosphere, 23.5 g of hafnium(IV) butoxide (M1) was dissolved in 25.5 g of a PGMEA / PGME (weight ratio 70 / 30) solution. While stirring, the reaction temperature was raised to 50°C, and 9.0 g of compound H1 was added dropwise to the aforementioned solution. After the dropwise addition, the reaction temperature was set to 60°C and stirring was continued for 2 hours. Then, a mixture obtained by suspending 24.2 g of compound G2 in 22.0 g of a PGMEA / PGME (weight ratio 70 / 30) solution was added to the aforementioned reaction system, and the reaction temperature was maintained at 60°C while stirring for 1 hour. After cooling to room temperature, the resulting reaction solution was filtered through a 0.45-μm PTFE filter to obtain a PGMEA / PGME solution of the metal-containing film-forming compound (A-10). The concentration of the components other than the solvent in the aforementioned solution was 22% by mass.

[0345] [Synthesis Example 12] Synthesis of Compound (A-11)

[0346] Using the above metal source M, the above compound group G, and the above compound group H at the feed rates shown in Table 2, in addition, the compound (A-11) shown in Table 2 was obtained under the same reaction conditions as in Synthesis Example 11.

[0347] [Table 2]

[0348]

[0349] [Synthesis Example 13] Synthesis of Metal-Containing Film-Forming Compound (A-12)

[0350] Under a nitrogen atmosphere, while stirring, a solution of 0.68 g of deionized water in 27.5 g of n-butanol was added dropwise over 2 hours at room temperature to 20.5 g of a solution of 23.5 g of hafnium(IV) n-butoxide (M1) in n-butanol. 9.8 g of compound (G1) was added to the resulting solution, and the mixture was stirred at room temperature for 30 minutes. The solution was concentrated under reduced pressure at 30 °C, further heated to 60 °C, and continuously heated under reduced pressure until no more distillate appeared. When no more distillate appeared, 45.0 g of a PGMEA / PGME (weight ratio 70 / 30) solution was added, and the mixture was heated at 40 °C under reduced pressure to obtain a PGMEA / PGME solution of the metal-containing film-forming compound (A-12). The concentration of the components other than the solvent in the aforementioned solution was 21% by mass.

[0351] [Synthesis Example 14] Synthesis of Compound (A-13)

[0352] Using the above metal source M and the above compound group G at the feed rates shown in Table 3, in addition, the compound (A-13) shown in Table 3 was obtained under the same reaction conditions as in Synthesis Example 13.

[0353] [Table 3]

[0354]

[0355] [Preparation of Metal-Containing Film-Forming Composition]

[0356] The crosslinking agents and acid generators used in the preparation of the metal-containing film-forming composition are as follows. [Crosslinking Agents XL-1 to XL-2]

[0357] The crosslinking agents (XL-1) to (XL-2) used in the metal-containing film-forming composition are as follows.

[0358] [Chemical Formula 25]

[0359]

[0360] [Acid Generator (D-1)]

[0361] The acid generator (D-1) used in the metal-containing film-forming composition is as follows.

[0362] [Chemical Formula 26]

[0363] (CH3CH2)3N + H

[0364] C4F9SO3 -

[0365] (D1)

[0366] [Preparation Example 1] Preparation of the metal-containing film-forming composition (UDL-1)

[0367] The metal-containing film-forming compound (A-1) was dissolved in a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) at the ratio shown in Table 4, and filtered through a 0.02-μm filter membrane to prepare the metal-containing film-forming composition (UDL-1).

[0368] [Preparation Examples 2 to 17] Preparation of the metal-containing film-forming compositions (UDL-2 to 16) and the metal-containing film-forming composition for comparative example (Comparative Example UDL-1)

[0369] The types and contents of the respective components were adjusted as shown in Table 4, and otherwise, the same operations as those for UDL-1 were carried out to prepare each liquid medicine. In addition, in Table 4, "-" indicates that the corresponding component was not used. The high-boiling solvent (F-1) used was ethylene glycol dibenzyl ether: boiling point 364°C.

[0370] [Table 4]

[0371]

[0372]

[0373] [Examples 1-1 to 1-16, Comparative Example 1-1]

[0374] [Patterning Test]

[0375] An organic underlayer film (ODL-301 manufactured by Shin-Etsu Chemical Co., Ltd.) was formed on a silicon wafer using a coating-type organic underlayer film material to obtain a Si substrate. Then, the above-prepared metal-containing film-forming compositions UDL-1 to 16 and Comparative Example UDL-1 were spin-coated on the aforementioned Si substrate and heated at 250°C for 60 seconds to obtain a metal-containing film with a film thickness of 20 nm.

[0376] Then, a resist material prepared by dissolving the following components in the proportions shown in Table 5 was spin-coated onto the metal-containing film, and pre-baked at 105 °C for 60 seconds using a hot plate to obtain a resist film with a thickness of 60 nm. It was exposed using an EUV scanning exposure machine NXE3300 (NA 0.33, σ 0.9 / 0.6, quadrupole illumination, mask with a hole pattern having a pitch of 46 nm and a +20% offset on the wafer) manufactured by ASML, and PEB was performed at 100 °C for 60 seconds on the hot plate, followed by development with a 2.38 mass% TMAH aqueous solution for 30 seconds to obtain a hole pattern with a size of 23 nm.

[0377] Using a length-measuring SEM (CG5000) manufactured by Hitachi High-Technologies Corporation, the exposure dose when the hole size was formed to be 23 nm was measured and defined as the sensitivity. Also, the sizes of 50 holes at this time were measured, and the size variation (CDU, 3σ) was calculated. The results are shown in Table 6.

[0378] [Chemical formula 27]

[0379]

[0380] [Chemical formula 28]

[0381]

[0382] · Surfactant: FC-4430 manufactured by 3M Company

[0383] [Table 5]

[0384]

[0385] · Organic solvent: PGMEA (propylene glycol monomethyl ether acetate) CyHO (cyclohexanone)

[0386] PGME (propylene glycol monomethyl ether)

[0387] [Table 6]

[0388]

[0389] As can be seen from the results shown in Table 6, when a metal-containing film having a crosslinkable group and a fluorine-substituted ligand formed from a metal-containing film-forming composition containing the metal-containing film-forming compound of the present invention is used as an antireflective coating intermediate film, pattern formation can be achieved with high sensitivity without deterioration of CDU (Examples 1-1 to 1-16). From this, it can be seen that the above antireflective coating intermediate film can contribute to the improvement of sensitivity while maintaining the LWR of the upper-layer resist. It is presumed that this is because it contains a metal atom with a large light absorption and a fluorine atom with a large light absorption, and an aromatic ring substituted with an organic group containing a crosslinking group, so that a metal-containing film with excellent heat resistance can be formed. During exposure in EUV lithography, excellent sensitization effects are exhibited due to secondary electrons generated therefrom.

[0390] On the other hand, when an antireflective coating intermediate film formed from a metal-containing film-forming composition containing a metal-containing film-forming compound having a fluorine atom in the ligand but no crosslinkable group is used, the result is poor sensitivity (Comparative Example 1-1).

[0391] As described above, the present invention can break the trade-off relationship between sensitivity and LWR, and can form an antireflective coating lower layer film or intermediate film that can contribute to the improvement of sensitivity while maintaining the LWR of the upper-layer resist. Therefore, it has high utility value in the field of EUV lithography.

[0392] This specification includes the following inventions.

[0393] [1]: A metal-containing film-forming compound, characterized in that:

[0394] The metal-containing film-forming compound contains at least one metal atom (a) selected from the group consisting of Ti, Zr, and Hf, and a multidentate ligand coordinated with the metal atom (a), and the multidentate ligand is substituted with a fluorine atom and is derived from a compound (b) having 1 to 50 carbon atoms containing one or more crosslinkable groups selected from vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, oxetanyl, nitrile, and vinylene.

[0395] [2]: The metal-containing film-forming compound according to [1] above, wherein the compound (b) contains any one of the structures represented by the following general formulas (b-1) to (b-4).

[0396] [Chemical formula 29]

[0397]

[0398] In the above general formula, R1 to R3 are hydrogen atoms or monovalent organic groups having 1 to 30 carbon atoms which may also contain a fluorine atom, vinyl group, allyl group, allyloxy group, ethynyl group, propargyl group, propargyloxy group, epoxy group, oxetanyl group, nitrile group, or vinylene group; R4 to R5 are hydrogen atoms or monovalent organic groups having 1 to 30 carbon atoms which may also contain a fluorine atom, vinyl group, allyl group, allyloxy group, ethynyl group, propargyl group, propargyloxy group, epoxy group, oxetanyl group, nitrile group, or vinylene group; R6 to R9 are hydrogen atoms or monovalent organic groups having 1 to 30 carbon atoms which may also contain a fluorine atom, vinyl group, allyl group, allyloxy group, ethynyl group, propargyl group, propargyloxy group, epoxy group, oxetanyl group, nitrile group, or vinylene group; and Y is a divalent organic group having 1 to 10 carbon atoms which may also contain a fluorine atom, vinyl group, allyl group, allyloxy group, ethynyl group, propargyl group, propargyloxy group, epoxy group, oxetanyl group, nitrile group, or vinylene group. In the above general formula (b-2), adjacent R4 and R5 may also be bonded to each other to form an unsaturated or saturated ring structure. The compounds of the above general formulae (b-1) to (b-4) contain at least one fluorine atom and at least one crosslinkable group selected from the group consisting of a vinyl group, allyl group, allyloxy group, ethynyl group, propargyl group, propargyloxy group, epoxy group, oxetanyl group, nitrile group, and vinylene group.

[0399] [3]: The metal-containing film-forming compound as described in the above [2], wherein the compound represented by the above general formulae (b-1) to (b-4) contains at least one of an aromatic ring, a heteroaromatic ring, and an alicyclic structure.

[0400] [4]: The metal-containing film-forming compound as described in the above [2] or [3], wherein the compound represented by the above general formulae (b-1) to (b-4) contains the structure represented by the following formula (1).

[0401] [Chemical 30]

[0402]

[0403] In the above formula, X m1 is a fluorine atom or a monovalent organic group having 1 to 10 carbon atoms containing a fluorine atom, R x is a monovalent organic group having 1 to 10 carbon atoms containing at least one crosslinkable group selected from the group consisting of a vinyl group, allyl group, allyloxy group, ethynyl group, propargyl group, propargyloxy group, epoxy group, oxetanyl group, nitrile group, and vinylene group, W is an organic group having 5 to 20 carbon atoms containing any one of an aromatic ring, a heteroaromatic ring, and an alicyclic structure, R Ais any one selected from linear alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and hydroxyl groups, s1 + s2 is 1 to 5, s1 is 0 to 5, s2 is 0 to 5, n2 is 0 to 2, and * is a bonding part.

[0404] [5]: A metal-containing film-forming compound as described in any one of [1] to [4] above, wherein the metal-containing film-forming compound further contains a ligand (c) derived from a silicon compound represented by the following general formula (2).

[0405] [Chemical formula 31]

[0406]

[0407] In the above general formula (2), R 3A , R 3B and R 3C are each an organic group having 1 to 30 carbon atoms selected from any one of crosslinking groups represented by the following general formulas (c-1) to (c-3), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or an aryl group having 1 to 20 carbon atoms.

[0408] [Chemical formula 32]

[0409]

[0410] In the above general formulas (c-1) to (c-3), R3 is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding part.

[0411] [6]: A metal-containing film-forming compound as described in any one of [2] to [4] above, wherein the metal-containing film-forming compound is a reaction product of a metal-containing compound selected from a metal compound represented by the following formula (3), a hydrolyzate, a condensate, and a hydrolyzate-condensate of the metal compound represented by the following formula (3), and a compound represented by any one of the above formulas (b-1) to (b-4).

[0412] [Chemical formula 33]

[0413] L a MX b (3)

[0414] In the formula, M is any one of Ti, Zr, and Hf. L is any one of monodentate ligands and polydentate ligands having 1 to 30 carbon atoms, and X is a hydrolyzable group selected from halogen atoms, alkoxy groups, carboxylate groups, acyloxy groups, -NR a R b . R a and R bEach is independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. a + b = 2 to 4, and a and b are integers from 0 to 4.

[0415] [7]: A metal-containing film-forming composition that functions as an underlayer film material or an intermediate film material for a resist used in semiconductor manufacturing, and is characterized by containing:

[0416] (A) A metal-containing film-forming compound as described in any one of the above [1] to [6], and

[0417] (B) An organic solvent.

[0418] [8]: The metal-containing film-forming composition as described in the above [7], wherein the composition further contains one or more of (C) a crosslinking agent, (D) an acid generator, and (E) a surfactant.

[0419] [9]: The metal-containing film-forming composition as described in the above [7] or [8], wherein the aforementioned (B) organic solvent is a mixture of one or more organic solvents with a boiling point below 180°C and one or more organic solvents with a boiling point of 180°C or higher ((B') high-boiling solvent).

[0420]

[10] : A pattern formation method, which is a method for forming a pattern on a substrate to be processed, and is characterized by having the following steps: (I-1) After coating the metal-containing film-forming composition as described in any one of the above [7] to [9] on the substrate to be processed, heat treatment is performed to thereby form a metal-containing film; (I-2) An upper resist film is formed on the aforementioned metal-containing film using a photoresist material; (I-3) After pattern exposure of the aforementioned upper resist film, development is performed with a developer to form a pattern on the aforementioned upper resist film; (I-4) Using the upper resist film having the aforementioned pattern as a mask, and transferring the pattern to the aforementioned metal-containing film by dry etching; and (I-5) Using the metal-containing film having the aforementioned pattern as a mask to process the aforementioned substrate to be processed, and forming a pattern on the aforementioned substrate to be processed.

[0421]

[11] : A pattern formation method, which is a method for forming a pattern on a substrate to be processed, is characterized by the following steps: (II-1) forming an organic resist lower layer film on the substrate to be processed; (II-2) coating the composition for forming a metal-containing film as described in any one of [7] to [9] above on the organic resist lower layer film and then performing heat treatment to form a metal-containing film; (II-3) forming a resist upper layer film using a photoresist material on the metal-containing film; (II-4) performing pattern exposure on the resist upper layer film and then developing it with a developer to form a pattern on the resist upper layer film; (II-5) using the resist upper layer film having the pattern formed thereon as a mask and transferring the pattern to the metal-containing film by dry etching; (II-6) using the metal-containing film having the pattern transferred thereon as a mask and transferring the pattern to the organic resist lower layer film by dry etching; and (II-7) processing the substrate to be processed using the organic resist lower layer film having the pattern formed thereon as a mask to form a pattern on the substrate to be processed.

[0422]

[12] : A pattern formation method, which is a method for forming a pattern on a substrate to be processed, is characterized by the following steps: (III-1) coating the composition for forming a metal-containing film as described in any one of [7] to [9] above on the substrate to be processed and then performing heat treatment to form a metal-containing film; (III-2) forming an inorganic hard mask intermediate film selected from a silicon-containing resist intermediate film, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film; (III-3) forming an organic thin film on the inorganic hard mask intermediate film; (III-4) forming a resist upper layer film using a photoresist material on the organic thin film; (III-5) performing pattern exposure on the resist upper layer film and then developing it with a developer to form a pattern on the resist upper layer film; (III-6) using the resist upper layer film having the pattern formed thereon as a mask and transferring the pattern to the organic thin film and the inorganic hard mask intermediate film by dry etching; (III-7) using the inorganic hard mask intermediate film having the pattern transferred thereon as a mask and transferring the pattern to the metal-containing film by dry etching; and (III-8) processing the substrate to be processed using the metal-containing film having the pattern formed thereon as a mask to form a pattern on the substrate to be processed.

[0423]

[13] : A pattern forming method, which is a method for forming a pattern on a substrate to be processed, characterized by the following steps: (IV-1) After coating the composition for forming a metal-containing film described in any one of [7] to [9] above on the substrate to be processed, heat treatment is performed to form a metal-containing film; (IV-2) An organic intermediate film is formed on the aforementioned metal-containing film; (IV-3) A silicon-containing resist intermediate film or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film is formed on the aforementioned organic intermediate film; (IV-4) A resist upper layer film is formed on the aforementioned silicon-containing resist intermediate film or the aforementioned organic thin film using a photoresist material; (IV-5) After pattern exposure of the aforementioned resist upper layer film, development is performed with a developer to form a pattern on the aforementioned resist upper layer film; (IV-6) Using the resist upper layer film having the aforementioned pattern as a mask, and transferring the pattern to the aforementioned silicon-containing resist intermediate film or the aforementioned organic thin film and the aforementioned inorganic hard mask intermediate film by dry etching; (IV-7) Using the silicon-containing resist intermediate film or the inorganic hard mask intermediate film having the aforementioned pattern transferred thereon as a mask, and transferring the pattern to the aforementioned organic intermediate film by dry etching; (IV-8) Using the aforementioned organic intermediate film as a mask, and transferring the pattern to the aforementioned metal-containing film by dry etching; and (IV-9) Using the metal-containing film having the aforementioned pattern formed thereon as a mask to process the aforementioned substrate to be processed, and forming a pattern on the aforementioned substrate to be processed.

[0424]

[14] : The pattern forming method as described in

[10] above, wherein in the aforementioned step (I-3), the aforementioned pattern exposure is performed using EUV light.

[0425]

[15] : The pattern forming method as described in

[11] above, wherein in the aforementioned step (II-4), the aforementioned pattern exposure is performed using EUV light.

[0426]

[16] : The pattern forming method as described in

[12] above, wherein in the aforementioned step (III-5), the aforementioned pattern exposure is performed using EUV light.

[0427]

[17] : The pattern forming method as described in

[13] above, wherein in the aforementioned step (IV-5), the aforementioned pattern exposure is performed using EUV light.

[0428] In addition, the present invention is not limited to the above embodiments. The above embodiments are illustrative, and those having substantially the same constitution as the technical idea described in the claims of the present invention and exhibiting the same effects are all included in the technical scope of the present invention.

[0429] Description of Reference Numerals

[0430] 1: Substrate to be processed

[0431] 1a: Pattern

[0432] 2: Organic resist underlayer film

[0433] 2a: Organic resist underlayer film pattern

[0434] 3: Metal-containing film

[0435] 3a: Metal-containing film pattern

[0436] 4: Resist upper layer film

[0437] 4a: Resist upper layer film pattern

[0438] 5: Mask

[0439] P: Exposure

Claims

1. A metal-containing film-forming compound, characterized in that: The metal-containing film-forming compound contains at least one metal atom (a) selected from the group consisting of Ti, Zr, and Hf, and a multidentate ligand coordinated to the metal atom (a), and The polydentate ligand is substituted with a fluorine atom and is derived from a compound (b) having 1 to 50 carbon atoms and containing one or more crosslinkable groups selected from the group consisting of vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, oxetanyl, nitrile and vinylene.

2. The metal-containing film-forming compound according to claim 1, wherein The compound (b) contains any one of the structures represented by the following general formulae (b-1) to (b-4); In the general formula, R1 to R3 are hydrogen atoms or monovalent organic groups having 1 to 30 carbon atoms which may contain fluorine atoms, vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, oxetanyl, nitrile, or vinylene groups; R4 to R5 are hydrogen atoms or monovalent organic groups having 1 to 30 carbon atoms which may contain fluorine atoms, vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, oxetanyl, nitrile, or vinylene groups; R6 to R9 are hydrogen atoms or monovalent organic groups having 1 to 30 carbon atoms which may contain fluorine atoms, vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, oxetanyl, nitrile, or vinylene groups; The general formula (b-2) is a monovalent organic group having 1 to 30 carbon atoms, and Y is a divalent organic group having 1 to 10 carbon atoms which may also contain a fluorine atom, a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyloxy group, an epoxy group, an oxetanyl group, a nitrile group, or a vinylidene group; in the general formula (b-2), adjacent R4 and R5 may also be bonded to each other to form an unsaturated or saturated ring structure; the compounds of the general formulas (b-1) to (b-4) contain at least one fluorine atom and at least one crosslinking group selected from the group consisting of a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyloxy group, an epoxy group, an oxetanyl group, a nitrile group, or a vinylidene group.

3. The metal-containing film-forming compound according to claim 2, wherein The compounds represented by the general formulae (b-1) to (b-4) contain at least one of an aromatic ring, a heteroaromatic ring, and an alicyclic structure.

4. The metal-containing film-forming compound according to claim 3, wherein The compounds represented by the general formulae (b-1) to (b-4) contain the structure represented by the following formula (1); In this formula, X m1 is a fluorine atom or a monovalent organic group having 1 to 10 carbon atoms and containing a fluorine atom, R x is a monovalent organic group having 1 to 10 carbon atoms and containing one or more crosslinkable groups selected from the group consisting of vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, oxetanyl, nitrile, and vinylene, W is an organic group having 5 to 20 carbon atoms and containing any one of an aromatic ring, a heteroaromatic ring, and an alicyclic structure, R A It is any one selected from a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a hydroxy group, s1+s2 is 1 to 5, s1 is 0 to 5, s2 is 0 to 5, n2 is 0 to 2, and * is a bonding portion.

5. The metal-containing film-forming compound according to claim 1, wherein The metal-containing film-forming compound further contains a ligand (c) derived from a silicon compound represented by the following general formula (2); In the general formula (2), R 3A , R 3B and R 3C Any one of an organic group having 1 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and an aryl group having 1 to 20 carbon atoms, which has a crosslinking group represented by any of the following general formulae (c-1) to (c-3); In the general formulae (c-1) to (c-3), R3 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.

6. The metal-containing film-forming compound according to claim 2, wherein The metal-containing film-forming compound is a reaction product of a metal compound represented by the following formula (3), a metal compound represented by the following formula (3), a hydrolyzate, a condensate, and a hydrolysis-condensate of the metal compound represented by the following formula (3), and a compound represented by any one of the formulas (b-1) to (b-4); L a MX b (3) In the formula, M is any one of Ti, Zr, and Hf; L is any one of a monodentate ligand and a multidentate ligand having 1 to 30 carbon atoms; X is selected from a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, -NR a R b The hydrolyzable group R a and R b Each is independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms; a+b=2 to 4, and a and b are integers of 0 to 4.

7. A metal-containing film-forming composition which functions as a resist underlayer film material or a resist intermediate film material used in semiconductor manufacturing, characterized in that it contains: (A) the metal-containing film-forming compound according to any one of claims 1 to 6, and (B) Organic solvent.

8. The metal-containing film-forming composition according to claim 7, wherein The composition further contains one or more of (C) a crosslinking agent, (D) an acid generator, and (E) a surfactant.

9. The metal-containing film-forming composition according to claim 7, wherein The (B) organic solvent is a mixture of one or more organic solvents having a boiling point of less than 180° C. and one or more organic solvents having a boiling point of 180° C. or higher ((B′) high boiling point solvent).

10. A method for forming a pattern on a processed substrate, characterized by comprising the following steps: (I-1) coating the metal-containing film-forming composition according to claim 7 on a substrate to be processed and then performing a heat treatment to form a metal-containing film, (I-2) forming a resist upper layer film on the metal-containing film using a photoresist material, (I-3) after exposing the resist upper layer film to pattern exposure, developing with a developer to form a pattern on the resist upper layer film, (I-4) using the resist upper layer film having the pattern as a mask, and transferring the pattern to the metal-containing film by dry etching, and (I-5) The substrate to be processed is processed using the metal-containing film on which the pattern is formed as a mask to form a pattern on the substrate to be processed.

11. A method for forming a pattern on a processed substrate, characterized by comprising the following steps: (II-1) forming an organic resist underlayer film on a substrate to be processed, (II-2) forming a metal-containing film by coating the metal-containing film-forming composition according to claim 7 on the organic resist underlayer film and then performing a heat treatment, (II-3) forming a resist upper layer film on the metal-containing film using a photoresist material, (II-4) after exposing the resist upper layer film to pattern exposure, developing with a developer to form a pattern on the resist upper layer film, (II-5) using the resist upper layer film having the pattern formed thereon as a mask, and transferring the pattern to the metal-containing film by dry etching, (II-6) using the metal-containing film to which the pattern is transferred as a mask, and transferring the pattern to the organic resist underlayer film by dry etching, and (II-7) The substrate to be processed is processed using the organic resist underlayer film having the pattern formed thereon as a mask to form a pattern on the substrate to be processed.

12. A method for forming a pattern on a processed substrate, characterized by comprising the following steps: (III-1) forming a metal-containing film by coating the metal-containing film-forming composition according to claim 7 on a substrate to be processed and then performing a heat treatment, (III-2) forming an inorganic hard mask intermediate film selected from a silicon-containing resist intermediate film, 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 exposing the resist upper layer film to pattern exposure, developing with a developer to form a pattern on the resist upper layer film, (III-6) using the resist upper layer film having the pattern as a mask, and transferring the pattern to the organic thin film and the inorganic hard mask intermediate film by dry etching, (III-7) using the inorganic hard mask intermediate film having the pattern transferred thereto as a mask, and transferring the pattern to the metal-containing film by dry etching, and (III-8) The substrate to be processed is processed using the metal-containing film on which the pattern is formed as a mask to form a pattern on the substrate to be processed.

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

14. The pattern forming method according to claim 10, wherein: In this step (I-3), EUV light is used to perform the pattern exposure.

15. The pattern forming method according to claim 11, wherein: In this step (II-4), EUV light is used to perform the pattern exposure.

16. The pattern forming method according to claim 12, wherein: In this step (III-5), EUV light is used to perform the pattern exposure.

17. The pattern forming method according to claim 13, wherein: In this step (IV-5), EUV light is used to perform the pattern exposure.

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