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 purpose of the present invention is to provide: a compound for forming a metal-containing film, which is used for forming a metal-containing film that can maintain the LWR of an upper resist and has improved sensitivity; a composition for forming a metal-containing film, which contains the compound; and a pattern forming method using the composition. A compound for forming a metal-containing film, characterized in that: the compound for forming a metal-containing film 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); the polydentate ligand is derived from a C1-50 compound (b) substituted with at least one halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom.

Description

Technical Field

[0001] The present invention relates to a metal-containing film-forming compound usable for fine patterning by a multilayer resist method in a semiconductor device manufacturing process, 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 progressed rapidly. In particular, logic devices used in smartphones and the like have driven miniaturization, and mass production of 10 nm node logic devices has been carried out using multiple exposure (multiple patterning lithography) processing by ArF lithography.

[0003] For subsequent lithography at the 7 nm node and 5 nm node, problems such as high cost due to multiple exposures and overlapping accuracy of 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, the contrast of the light in EUV lithography is high, and high resolution can be expected. Since EUV has a short wavelength and a high energy density, it can sensitize an acid generator with a small number of photons. The number of photons in EUV exposure is said to be 1 / 14 of that in ArF exposure. In EUV exposure, deterioration of line width roughness (LWR) and critical dimension uniformity (CDU) due to photon deviation is regarded as a problem (Non-Patent Document 1). Also, it has been pointed out that concentration, aggregation of the base polymer and acid generator, and diffusion of acid generated from the acid generator may have an impact.

[0005] As a countermeasure, for example, LWR can be reduced by lowering the post-exposure bake (PEB) temperature, but the sensitivity of the EUV resist also decreases. Also, increasing the addition amount of a quencher also reduces LWR, but this method also reduces the sensitivity. 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 make EUV lithography practical for mass production processes of semiconductor devices, numerous problems need to be solved. However, among these, the characteristic that particularly needs to be improved is to increase the sensitivity while maintaining the LWR.

[0011] In view of the above situation, an object of the present invention is to provide a metal-containing film-forming compound for forming a metal-containing film that can maintain the LWR of the upper resist and contribute to an increase in sensitivity, a metal-containing film-forming composition containing this compound, and a patterning method using this composition.

[0012] [Means for Solving the Problem]

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

[0014] The aforementioned 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 aforementioned metal atom (a), and

[0015] the aforementioned multidentate ligand is derived from a compound (b) having 1 to 50 carbon atoms substituted with at least one halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom.

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

[0017] Furthermore, it is preferable that the aforementioned compound (b) contains any of the structures represented by the following general formulas (b-1) to (b-4).

[0018] [Chemical Formula 1]

[0019]

[0020] In the above general formulas, R1 to R3 are a hydrogen atom, or a monovalent organic group having 1 to 30 carbon atoms that may contain any of a chlorine atom, a bromine atom, and an iodine atom, R4 to R5 are a hydrogen atom, or a monovalent organic group having 1 to 30 carbon atoms that may contain any of a chlorine atom, a bromine atom, and an iodine atom, R6 to R9 are a hydrogen atom, or a monovalent organic group having 1 to 30 carbon atoms that may contain any of a chlorine atom, a bromine atom, and an iodine atom, and Y is a divalent organic group having 1 to 10 carbon atoms. 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 formulas (b-1) to (b-4) contain at least one or more of a chlorine atom, a bromine atom, and an iodine atom.

[0021] In the case of such a metal-containing film-forming compound, a resist underlayer film or an intermediate film-forming composition that can maintain the LWR of the upper resist and contribute to the improvement of sensitivity can be obtained.

[0022] At this time, it is preferable that the compound represented by the general formulas (b-1) to (b-4) contains at least one or more of an aromatic ring, a heteroaromatic ring, and an alicyclic structure.

[0023] In the case of such a metal-containing film-forming compound, due to excellent heat resistance, the amount of sublimates during the formation of a metal oxide film can be reduced, and a metal oxide film containing a large amount of chlorine atoms, bromine atoms, and iodine atoms can be formed.

[0024] At this time, it is preferable that the compound represented by the general formulas (b-1) to (b-4) contains the structure represented by the following formula (1).

[0025] [Chemical formula 2]

[0026]

[0027] In the above formula, X m1 is any one of a chlorine atom, a bromine atom, and an iodine atom, or a monovalent organic group having 1 to 10 carbon atoms containing any one of a chlorine atom, a bromine atom, and an iodine atom, 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 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a halogen atom, and a halogenated alkyl group having 1 to 10 carbon atoms, s is 1 to 5, and n1 is 0 to 2.

[0028] In the case of such a metal-containing film-forming compound, due to excellent heat resistance, the amount of sublimates during the formation of a metal oxide film can be reduced and a metal oxide film containing a large amount of chlorine atoms, bromine atoms, and iodine atoms can be formed.

[0029] Furthermore, it is preferable that the metal-containing film-forming compound 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 crosslinking group having the structures represented by the following general formulas (c-1) to (c-3), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and 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 become a metal-containing film-forming compound with excellent stability, and can improve the storage life stability of the resist underlayer film or intermediate film-forming composition.

[0037] Furthermore, it is preferable that the aforementioned metal-containing film-forming compound further contains a ligand having one or more crosslinkable groups selected from vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, and oxetanyl.

[0038] At this time, it is preferable that the aforementioned compound (b) further has one or more crosslinkable groups selected from vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, and oxetanyl.

[0039] If it is such a metal-containing film-forming compound, due to its more excellent heat resistance, the amount of sublimates during the formation of the metal oxide film can be reduced, and a metal oxide film containing a large amount of chlorine atoms, bromine atoms, and iodine atoms can be formed.

[0040] Furthermore, it is preferable that the aforementioned metal-containing film-forming compound is a reaction product of one or more metal-containing compounds selected from the metal compounds represented by the following formula (3), and the hydrolyzates, condensates, and hydrolytic condensates of the metal compounds represented by the following formula (3) and any one of the compounds represented by the aforementioned formulas (b-1) to (b-4).

[0041] [Chemical Formula 5]

[0042] L a MX b (3)

[0043] 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, carboxyl groups, acyloxy groups, -NR a R b Among them. 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.

[0044] By using such a metal compound, a metal-containing film having better dry etching resistance to fluorine gas and oxygen can be formed.

[0045] Furthermore, it is preferable that the aforementioned compound (b) contains one or more chlorine atoms.

[0046] If it is such a compound for forming a metal-containing film, a composition for forming an underlayer film or an intermediate film of a resist, which can maintain the LWR of the upper-layer resist and contribute to the improvement of sensitivity, can be obtained.

[0047] Furthermore, it is preferable that the aforementioned compound (b) contains one or more bromine atoms.

[0048] If it is such a compound for forming a metal-containing film, a composition for forming an underlayer film or an intermediate film of a resist, which can maintain the LWR of the upper-layer resist and contribute to the improvement of sensitivity, can be obtained.

[0049] Furthermore, it is preferable that the aforementioned compound (b) contains one or more iodine atoms.

[0050] If it is such a compound for forming a metal-containing film, a composition for forming an underlayer film or an intermediate film of a resist, which can maintain the LWR of the upper-layer resist and contribute to the improvement of sensitivity, can be obtained.

[0051] Furthermore, the present invention provides a composition for forming a metal-containing film, which is a composition for forming a metal-containing film that functions as an underlayer film material or an intermediate film material of a resist used in semiconductor manufacturing, and contains:

[0052] (A) The aforementioned compound for forming a metal-containing film, and

[0053] (B) An organic solvent.

[0054] If it is such a composition for forming a metal-containing film, an underlayer film or an intermediate film of a resist, which can maintain the LWR of the upper-layer resist and contribute to the improvement of sensitivity, can be formed.

[0055] Furthermore, the aforementioned composition may further contain one or more of (C) a crosslinking agent, (D) an acid generator, and (E) a surfactant.

[0056] 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 having better coating properties, dry etching resistance, and filling and / or planarization characteristics.

[0057] Furthermore, it is preferable that the aforementioned (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 solvent).

[0058] By adding a high-boiling solvent to the above metal-containing film-forming compound to impart fluidity, it is possible to suppress the occurrence of coating defects caused by the drying of the metal-containing film-forming composition.

[0059] Furthermore, the present invention provides a patterning method, which is a method for forming a pattern on a substrate to be processed, and has the following steps:

[0060] (I-1) On the substrate to be processed, after coating the above metal-containing film-forming composition, a metal-containing film is formed by heat treatment,

[0061] (I-2) An upper resist film is formed on the aforementioned metal-containing film using a photoresist material,

[0062] (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,

[0063] (I-4) Using the aforementioned patterned upper resist film as a mask, the pattern is transferred to the aforementioned metal-containing film by dry etching, and

[0064] (I-5) Using the aforementioned patterned metal-containing film as a mask, the aforementioned substrate to be processed is processed to form a pattern on the aforementioned substrate to be processed.

[0065] By using the above two-layer resist treatment for the patterning method, a fine pattern can be formed on the object to be processed (substrate to be processed).

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

[0067] (II-1) An organic lower resist film is formed on the substrate to be processed,

[0068] (II-2) After coating the above metal-containing film-forming composition on the aforementioned organic lower resist film, a metal-containing film is formed by heat treatment,

[0069] (II-3) An upper resist film is formed on the aforementioned metal-containing film using a photoresist material,

[0070] (II-4) 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,

[0071] (II-5) Using the aforementioned patterned upper resist film as a mask, the pattern is transferred to the aforementioned metal-containing film by dry etching,

[0072] (II-6) Using the aforementioned metal-containing film with the transferred pattern as a mask, the pattern is transferred to the aforementioned organic lower resist film by dry etching, and

[0073] (II-7) Using the aforementioned organic resist lower layer film with the formed pattern as a mask, processing the aforementioned substrate to be processed to form a pattern on the aforementioned substrate to be processed.

[0074] With the pattern formation method using the above three-layer resist treatment, a fine pattern can be formed on the object to be processed with high precision.

[0075] Furthermore, the present invention provides a pattern formation method, which is a method for forming a pattern on a substrate to be processed, and has the following steps:

[0076] (III-1) On the substrate to be processed, after coating the aforementioned composition for forming a metal-containing film, forming a metal-containing film by heat treatment.

[0077] (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 aforementioned metal-containing film.

[0078] (III-3) Forming an organic thin film on the aforementioned inorganic hard mask intermediate film.

[0079] (III-4) Using a photoresist material to form a resist upper layer film on the aforementioned organic thin film.

[0080] (III-5) After subjecting the aforementioned resist upper layer film to pattern exposure, developing it with a developer to form a pattern on the aforementioned resist upper layer film.

[0081] (III-6) Using the aforementioned resist upper layer film with the formed pattern as a mask, transferring the pattern to the aforementioned organic thin film and the aforementioned inorganic hard mask intermediate film by dry etching.

[0082] (III-7) Using the aforementioned inorganic hard mask intermediate film with the transferred pattern as a mask, transferring the pattern to the aforementioned metal-containing film by dry etching, and

[0083] (III-8) Using the aforementioned metal-containing film with the formed pattern as a mask, processing the aforementioned substrate to be processed to form a pattern on the aforementioned substrate to be processed.

[0084] With the pattern formation method using the above four-layer resist treatment, a fine pattern can be formed on the object to be processed with high precision.

[0085] Furthermore, the present invention provides a pattern formation method, which is a method for forming a pattern on a substrate to be processed, and has the following steps:

[0086] (IV-1) On the substrate to be processed, after coating the aforementioned composition for forming a metal-containing film, forming a metal-containing film by heat treatment.

[0087] (IV-2) Form an organic intermediate film on the aforementioned metal-containing film.

[0088] (IV-3) Form 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, on the aforementioned organic intermediate film.

[0089] (IV-4) Use a photoresist material to form a resist upper layer film on the aforementioned silicon-containing resist intermediate film or the aforementioned organic thin film.

[0090] (IV-5) After performing pattern exposure on the aforementioned resist upper layer film, develop it with a developer to form a pattern on the aforementioned resist upper layer film.

[0091] (IV-6) Use the aforementioned patterned resist upper layer film as a mask, and transfer 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.

[0092] (IV-7) Use the aforementioned patterned silicon-containing resist intermediate film or inorganic hard mask intermediate film as a mask, and transfer the pattern to the aforementioned organic intermediate film by dry etching.

[0093] (IV-8) Use the aforementioned organic intermediate film as a mask, and transfer the pattern to the aforementioned metal-containing film by dry etching, and

[0094] (IV-9) Use the aforementioned patterned metal-containing film as a mask, and process the aforementioned substrate to be processed to form a pattern on the aforementioned substrate to be processed.

[0095] With the pattern formation method using the above multi-layer resist treatment, a fine pattern can be formed with high precision on the object to be processed.

[0096] Also, in the aforementioned step (I-3), it is preferable to perform the aforementioned pattern exposure using EUV light.

[0097] Also, in the aforementioned step (II-4), it is preferable to perform the aforementioned pattern exposure using EUV light.

[0098] Also, in the aforementioned step (III-5), it is preferable to perform the aforementioned pattern exposure using EUV light.

[0099] Also, in the aforementioned step (IV-5), it is preferable to perform the aforementioned pattern exposure using EUV light.

[0100] The compound for forming a metal-containing film of the present invention, since it contains not only metal atoms with large light absorption but also chlorine atoms, bromine atoms, or iodine atoms with large light absorption, can form a resist lower layer film or intermediate film that can maintain the LWR of the upper resist in EUV lithography and contribute to the improvement of sensitivity.

[0101] (Effects of the Invention)

[0102] The metal-containing compound for film formation of the present invention contains, in addition to metal atoms with high light absorption, any one of chlorine atoms, bromine atoms, and iodine atoms with high light absorption, and has the characteristic that an intensifying effect can be expected from secondary electrons generated during exposure in EUV lithography.

[0103] Furthermore, the metal-containing film obtained in the present invention can achieve high etching selectivity with respect to organic materials. Therefore, the formed photoresist pattern can be sequentially transferred to the metal-containing film, the organic underlayer film, or the CVD organic hard mask using dry etching. Especially in recent years' semiconductor device manufacturing processes where miniaturization has advanced, in order to prevent pattern collapse after development, the thickness of the photoresist film tends to be thinned, making it increasingly difficult to transfer the pattern to the underlayer resist film. However, if the metal-containing film-forming composition of the present invention is used, even when a thin photoresist film is used as an etching mask, deformation of the photoresist pattern during dry etching can be suppressed, and this pattern can be transferred to the substrate with high precision. BRIEF DESCRIPTION OF THE DRAWINGS

[0104] Figure 1 (I-A) to (I-I) show a flowchart of the pattern formation method of the present invention. DETAILED DESCRIPTION

[0105] As described above, there is a need to develop a metal-containing compound for film formation, a metal-containing film-forming composition containing this compound, and a pattern formation method using this composition, which are used to form an underlayer resist film or an intermediate film that can maintain the LWR of the upper resist and contribute to the improvement of sensitivity.

[0106] The inventors of the present application made diligent investigations to achieve the above object. As a result, it was found that by introducing any one of chlorine atoms, bromine atoms, and iodine atoms into the metal-containing compound for film formation, the sensitivity can be improved without deteriorating the LWR of the upper resist, and thus the present invention was completed.

[0107] That is, the present invention is a metal-containing compound for film formation. The metal-containing compound for film formation 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). The multidentate ligand is derived from a compound (b) having 1 to 50 carbon atoms substituted with at least one halogen atom selected from the group consisting of chlorine atoms, bromine atoms, and iodine atoms.

[0108] The following is a detailed description of the present invention, but the present invention is not limited thereto.

[0109] <Metal-Containing Compound for Film Formation>[[]]END]]

[0110] 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 metal atom (a), and the multidentate ligand is derived from a compound (b) having 1 to 50 carbon atoms substituted with at least one halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom.

[0111] The metal-containing compound for film formation of the present invention is characterized in that the metal-containing compound for film formation contains the following constitution.

[0112] (a) At least one metal atom selected from the group consisting of Ti, Zr, and Hf.

[0113] (b) A multidentate ligand derived from a compound (b) having 1 to 50 carbon atoms substituted with at least one halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom.

[0114] 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 preferably contains any one of Ti, Zr, and Hf. From the viewpoints of productivity and improvement of the sensitivity of the resist, it is more preferably any one of Ti or Hf.

[0115] The ligand coordinated to the metal-containing compound for film formation may also contain different structures, and may contain a ligand conforming to the above constitution (b) and other general ligands.

[0116] The above compound (b) is preferably any one of the structures represented by the following general formulas (b-1) to (b-4).

[0117] [Chemical Formula 6]

[0118]

[0119] In the above general formulas, R1 to R3 are a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms which may contain any one of a chlorine atom, a bromine atom, and an iodine atom; R4 to R5 are a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms which may contain any one of a chlorine atom, a bromine atom, and an iodine atom; R6 to R9 are a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms which may contain any one of a chlorine atom, a bromine atom, and an iodine atom; and Y is a divalent organic group having 1 to 10 carbon atoms. In the above general formula (b-2), adjacent R4 and R5 may be bonded 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 of a chlorine atom, a bromine atom, and an iodine atom.

[0120] The metal-containing film-forming compound of the present invention contains a chlorine atom, a bromine atom, or an iodine atom in a multidentate ligand having excellent coordination ability for a metal atom. Therefore, when it is used in a metal-containing film-forming composition, a metal-containing film containing a large amount of halogen atoms can be formed.

[0121] Furthermore, it is preferable that the compound represented by the general formula (b-1) to (b-4) contains at least one of an aromatic ring, a heteroaromatic ring, and an alicyclic structure.

[0122] The halogen atom-containing compound (b) used as the ligand has a higher heat resistance of the ligand containing a chlorine atom, a bromine atom, or an iodine atom due to containing the above structure. Therefore, when it is used in a metal-containing film-forming composition, a metal-containing film containing a large amount of chlorine atoms, bromine atoms, or iodine atoms can be formed.

[0123] It is preferable that the compound represented by the general formula (b-1) to (b-4) contains the structure represented by the following formula (1).

[0124] [Chemical formula 7]

[0125]

[0126] In the above formula, X m1 is any one of a chlorine atom, a bromine atom, an iodine atom, or a monovalent organic group having 1 to 10 carbon atoms containing any one of a chlorine atom, a bromine atom, and an iodine atom, 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 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a halogen atom, and a halogenated alkyl group having 1 to 10 carbon atoms, s is 1 to 5, and n1 is 0 to 2.

[0127] In the above formula (1), X m1 is any one of a chlorine atom, a bromine atom, an iodine atom, or a monovalent organic group having 1 to 10 carbon atoms containing any one of a chlorine atom, a bromine atom, and an iodine atom. Preferably, it is any one of a chlorine atom, a bromine atom, an iodine atom, or a halogenated hydrocarbon group having 1 to 10 carbon atoms containing any one of a chlorine atom, a bromine atom, and an iodine atom. Specific examples of the halogenated hydrocarbon group include halogenated alkyl groups such as chloromethyl, bromoethyl, and iodoethyl. When the above X m1 contains a plurality of halogen atoms, the plurality of halogen atoms may be the same or different.

[0128] In the above formula (1), R A is preferably a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms.

[0129] In the above formula (1), it is preferable that W is an organic group having 5 to 20 carbon atoms containing any of an aromatic ring, a heteroaromatic ring, and an alicyclic structure, and more preferably has the following structure.

[0130] [Chemical Formula 8]

[0131]

[0132] In the above formula, R x is any one of the above R A , X m1 , and * is a bonding part.

[0133] From the viewpoint of heat resistance, it is more preferable that W contains an aromatic ring in the above formula (1), and from the viewpoint of productivity, a benzene ring is particularly preferable.

[0134] Preferable examples of the structures represented by the above formulas (b-1) to (b-4) are listed below.

[0135] [Chemical Formula 9]

[0136]

[0137] In the above formula, X m1 and s have the same meaning as in the above formula (1), Z in the above formula is either an oxygen atom or a secondary amine, and any hydrogen atom in the above formula can also be substituted or unsubstituted by a saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms.

[0138] [Chemical Formula 10]

[0139]

[0140] In the above formula, X m1 and s have the same meaning as in the above formula (1), Z in the above formula is either an oxygen atom or a secondary amine, and any hydrogen atom in the above formula can also be substituted or unsubstituted by a saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms.

[0141] [Chemical Formula 11]

[0142]

[0143] In the above formula, X m1 and s have the same meaning as in the above formula (1), Z in the above formula is either an oxygen atom or a secondary amine, and any hydrogen atom in the above formula can also be substituted or unsubstituted by a saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms.

[0144] [Chemical Formula 12]

[0145]

[0146] In the above formula, X m1 is synonymous with s and the above formula (1), Y is synonymous with the above formula (b-4), and any hydrogen atom in the above formula may also be substituted or unsubstituted saturated or unsaturated monovalent organic groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, or substituted or unsubstituted aralkyl groups having 7 to 31 carbon atoms.

[0147] Preferably, the compounds represented by the above general formulas (b-1) to (b-4) contain one or more chlorine atoms, bromine atoms, or iodine atoms, more preferably bromine atoms or iodine atoms, and even more preferably iodine atoms.

[0148] In the case of such a metal-containing film-forming compound, due to the presence of chlorine atoms, bromine atoms, or iodine atoms with large light absorption, a sensitizing effect obtained from secondary electrons generated therefrom during exposure in EUV lithography can be more expected.

[0149] In particular, iodine atoms are ideal because they have a large atomic weight, a high effect of suppressing the diffusion of acid from the upper resist to the lower resist film, and the characteristics of being able to maintain the LWR originally possessed by the upper resist film and being highly sensitive.

[0150] Furthermore, the metal-containing film-forming compound of the present invention preferably further contains a ligand having one or more crosslinkable groups selected from vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, and oxetanyl. Among them, the compound (b), especially the compound represented by the above general formulas (b-1) to (b-4), more preferably has at least one or more of the above crosslinkable groups.

[0151] For the compound (b) using a ligand containing a chlorine atom, a bromine atom, or an iodine atom, by further containing a crosslinkable group, the heat resistance of the above halogen atom-containing ligand is improved. Therefore, when it is used in a metal-containing film-forming composition, a metal-containing film containing a large amount of the above halogen atoms can be formed.

[0152] One or more crosslinkable groups selected from vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, and oxetanyl are monovalent organic groups having 2 to 20 carbon atoms containing a crosslinkable group selected from vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, and oxetanyl. Specifically, the following structures are preferred.

[0153] [Chemical Formula 13]

[0154]

[0155] 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.

[0156] [Chemical formula 14]

[0157]

[0158] In the above general formula, R b is a hydrogen atom or a methyl group, and these may be the same or different in the same formula. R c is a hydrogen atom or a substituted or unsubstituted saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms, and * represents a bonding site.

[0159] [Chemical formula 15]

[0160]

[0161] In the formula, R e is a hydrogen atom or an organic group having 1 to 10 carbon atoms, and * represents a bonding site.

[0162] Furthermore, the metal-containing film-forming compound of the present invention is preferably a reaction product of a metal compound represented by the following formula (3), and a hydrolyzate, condensate, or hydrolyzate-condensate of the metal compound represented by the following formula (3) (hereinafter referred to as (a') metal-containing compound) and a compound represented by any one of the above formulas (b-1) to (b-4).

[0163] [Chemical formula 16]

[0164] L a MX b (3)

[0165] 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, carboxyl groups, acyloxy groups, -NR a R b and the like. 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.

[0166] When 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.

[0167] [(a’) Metal-containing compound]

[0168] (Hydrolyzable group)

[0169] The hydrolyzable group X in the above formula (3), such as a halogen atom, an alkoxy group, a carboxyl group, an acyloxy group, and -NR a R b 。R a And R b Are each independently preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

[0170] The above-mentioned halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.

[0171] The above-mentioned alkoxy group, such as a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a tert-butoxy group, etc.

[0172] The above-mentioned carboxyl group, such as an acetic acid group, a propionic acid group, a butyric acid group, a n-caproic acid group, a n-caprylic acid group, etc.

[0173] The above-mentioned acyloxy group, such as an acetoxy group, an ethynoxy group, a propionyloxy group, a butyryloxy group, a tert-butyryloxy group, a tert-pentyryloxy group, a n-caproyloxy group, a n-capryloxy group, etc.

[0174] The above-mentioned -NR a R b , such as an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dipropylamino group, etc.

[0175] The above-mentioned hydrolyzable group X is preferably an alkoxy group, more preferably an isopropoxy group, a n-butoxy group, or a tert-butoxy group.

[0176] (Monodentate ligand)

[0177] The above-mentioned monodentate ligand L, such as: a hydroxide ligand, a carboxyl ligand, an amide ligand, an amine ligand, an ammonia ligand, an olefin ligand, etc.

[0178] The above-mentioned amide ligand, such as: an unsubstituted amide ligand (NH2), a methylamide ligand (NHMe), a dimethylamide ligand (NMe2), a diethylamide ligand (NEt2), a dipropylamide ligand (NPr2), etc.

[0179] The above-mentioned amine ligand, such as: pyridine, a trimethylamine ligand, a piperidine ligand, etc.

[0180] The olefin ligand, such as: linear olefins such as ethylene and propylene, cyclic olefins such as cyclopentene, cyclohexene, and norbornene, etc.

[0181] (Polydentate ligand)

[0182] The above-mentioned multidentate ligand L, for example: ligands derived from hydroxy acid esters, ligands derived from β-diketones, ligands derived from β-keto esters, ligands derived from α,α-dicarboxylic esters, hydrocarbons having π bonds, diphosphines, etc.

[0183] The above-mentioned hydroxy acid esters, such as glycolate, lactate, 2-hydroxycyclohexane-1-carboxylate, salicylate, etc.

[0184] The above-mentioned β-diketones, such as acetoacetate, α-alkyl-substituted acetoacetate, β-ketovalerate, benzoylacetate, 1,3-acetonedicarboxylate, etc.

[0185] The above-mentioned α,α-dicarboxylic esters, such as diethyl malonate, α-alkyl-substituted diethyl malonate, α-cycloalkyl-substituted diethyl malonate, α-aryl-substituted diethyl malonate, etc.

[0186] The above-mentioned hydrocarbons having π bonds, such as chain dienes like butadiene and isoprene, cyclic dienes like cyclopentadiene, methylcyclopentadiene, pentamethylcyclopentadiene, cyclohexadiene, norbornadiene, etc., and aromatic hydrocarbons like benzene, toluene, xylene, hexamethylbenzene, naphthalene, indene, etc.

[0187] The above-mentioned diphosphines, such as 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, etc.

[0188] In the above general formula (3), a + b = 2 to 4, and a and b are integers from 0 to 4. It is more preferable that a is from 0 to 4, and 2 or 4 is even more preferable. It is more preferable that b is from 0 to 4, and 0 or 2 or 4 is even more preferable. 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.

[0189] Preferred examples of the metal compound represented by formula (3) are listed below.

[0190] For titanium-containing compounds, examples include bis(2,4-pentanedionato)diisopropoxytitanium(IV), tetra-n-butoxytitanium(IV), tetra-n-propoxytitanium(IV), tetra-isopropoxytitanium(IV), tri-n-butoxymonostearoyltitanium(IV), butoxytitanium(IV) oligomer, aminopropyltrimethoxytitanium(IV), triethoxymono(2,4-pentanedionato)titanium(IV), tri-n-propoxymono(2,4-pentanedionato)titanium(IV), triisopropoxymono(2,4-pentanedionato)titanium, di-n-butoxybis(2,4-pentanedionato)titanium(IV), etc.

[0191] Examples of the zirconium compound include bis(ethylacetoacetato)dibutoxyzirconium(IV), bis(2,4-pentanedionato)dibutoxyzirconium(IV), tetrabutoxyzirconium(IV), tetrapropoxyzirconium(IV), tetraisopropoxyzirconium(IV), aminopropyltriethoxyzirconium(IV), 2-(3,4-epoxycyclohexyl)ethyltrimethoxyzirconium(IV), γ-glycidoxypropyltrimethoxyzirconium(IV), 3-isocyanatopropyltrimethoxyzirconium(IV), triethoxymono(2,4-pentanedionato)zirconium(IV), tri-n-propoxymono(2,4-pentanedionato)zirconium(IV), triisopropoxymono(2,4-pentanedionato)zirconium(IV), tris(3-methacryloxypropyl)methoxyzirconium(IV), tris(3-acryloxypropyl)methoxyzirconium(IV), and the like.

[0192] Examples of the hafnium compound include bis(2,4-pentanedionato)diisopropoxyzirconium(IV), tetrabutoxyhafnium(IV), tetraisopropoxyhafnium(IV), tetraethoxyhafnium(IV), dichlorobis(cyclopentadienyl)hafnium(IV), and the like.

[0193] Among them, metal alkoxides, metal carboxylates, and metal acetates are more preferable.

[0194] In the synthesis reaction of the metal-containing film-forming compound, in addition to the (a') metal compound, a compound that can be a monodentate ligand or a polydentate ligand in the metal-containing film-forming compound (hereinafter referred to as the (b') ligand-forming compound) can also be added.

[0195] Examples of the above (b') ligand-forming compound include organic compounds such as the hydroxyl ligand, carboxyl ligand, amide ligand, amine ligand, ammonia ligand, and olefin ligand listed for L in the above general formula (3), ligands from hydroxy acid esters, ligands from β-diketones, ligands from β-keto esters, ligands from α,α-dicarboxylic acid esters, and the like. In addition, compounds having a plurality of hydroxyl groups can be cited.

[0196] In the metal-containing film-forming compound of the present invention, the content of the structural ligands represented by the above formulas (b-1) to (b-4) is preferably 10 mol% to 90 mol% of the total amount of the ligands coordinated to the metal atom, more preferably 20 mol% to 80 mol%, and still more preferably 25 mol% to 75 mol%. Ligands other than the compounds represented by the above formulas (b-1) to (b-4), such as the (b') above ligand-forming compound and ligands of alkoxy groups having 1 to 10 carbon atoms, are preferably 0 mol% to 90 mol% of the total amount of the ligands coordinated to the metal atom, and more preferably 20 mol% to 80 mol%.

[0197] Furthermore, during the synthesis reaction of the metal-containing film-forming compound of the present invention, a (c) silicon-containing compound may be added in addition to the (b') ligand-forming compound.

[0198] By replacing 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.

[0199] (c) The silicon-containing compound, for example, has a structure represented by the following formula (2).

[0200] [Chemical Formula 17]

[0201]

[0202] 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 crosslinking group having a structure represented by the following general formula (c-1) to (c-3), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or an organic group of an aryl group having 1 to 20 carbon atoms.

[0203] [Chemical Formula 18]

[0204]

[0205] In the above general formula (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.

[0206] It is more preferable that the silicon-containing compound is any of the following compounds, and from the viewpoint of productivity, trimethylsilanol is more ideal.

[0207] [Chemical Formula 19]

[0208]

[0209] 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 a (c) silicon-containing compound, 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) is preferably 10 mol% to 100 mol% of the total ligands coordinated to the metal atom, more preferably 20 mol% to 80 mol%, and still more preferably 25 mol% to 75 mol%. The ligand derived from the (c) silicon-containing compound is preferably 10 mol% to 90 mol% of the total ligands coordinated to the metal atom, more preferably 20 mol% to 80 mol%, and still more preferably 25 mol% to 75 mol%. Ligands other than the (b') ligand-forming compound and the (c) silicon-containing compound, such as ligands derived from alkoxy groups having 1 to 10 carbon atoms, are preferably 0 mol% to 90 mol% of the total ligands coordinated to the metal atom, and more preferably 0 mol% to 75 mol%.

[0210] The synthesis method of the metal-containing film-forming compound of the present invention is not particularly limited. For example, as the (a') metal-containing compound, a metal alkoxide, a metal carboxylate, or a metal acetylacetonate (acac) can be used, and the alkoxy group, carboxyl group, or acac metal can be reacted with the ligand derived from the compound represented by the above formulas (b-1) to (b-4) to obtain it. After hydrolytic condensation of the (a') metal-containing compound, it can be reacted with the ligand derived from the compound represented by the above formulas (b-1) to (b-4), or the (a') metal-containing compound can be reacted with the ligand derived from the compound represented by the above formulas (b-1) to (b-4) and then hydrolytically condensed. When hydrolytic condensation is difficult to control, it can be reacted with the ligand derived from the compound represented by the above formulas (b-1) to (b-4) in a non-aqueous environment. They are preferably appropriately adjusted according to the properties necessary for the metal-containing film-forming compound and the metal-containing film of the present invention. When the (c) silicon-containing compound and the compound represented by the above formulas (b-1) to (b-4) are used as ligands, it is preferred to react the (a') metal-containing compound with the (c) silicon-containing compound and then react with the ligand derived from the compound represented by the above formulas (b-1) to (b-4).

[0211] Regarding the method of performing a hydrolytic condensation reaction using the (a') metal-containing compound, for example, a method of performing a hydrolytic condensation reaction of the (a') metal-containing compound in an aqueous solvent, etc. In this case, other compounds having a hydrolyzable group can be added as needed. Also, an acid such as acetic acid can be added as a catalyst for the hydrolytic condensation reaction. The lower limit of the amount of water used in this hydrolytic condensation reaction is preferably 0.2 times the molar amount relative to the hydrolyzable group possessed by the (a') metal-containing compound, etc., more preferably 1 time the molar amount, and still more preferably 3 times the molar amount. The upper limit of the amount of the above water is preferably 20 times the molar amount, more preferably 15 times the molar amount, and still more preferably 10 times the molar amount.

[0212] 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 for the following (B) organic solvents can be used. General solvents and solvent mixtures contain ester, ether or alcohol functional groups. For example, a mixture of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) at a volume ratio of 70 / 30. Other solvents that can be used include, for example, butylene glycol monomethyl ether, ethylene glycol monomethyl ether, butylene glycol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butylene glycol 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.

[0213] <Metal-containing film-forming composition>

[0214] Furthermore, the present invention provides a metal-containing film-forming composition, which is a metal-containing film-forming composition that functions as an anti-resist underlayer film material or an anti-resist intermediate film material used in semiconductor manufacturing, and contains (A) the above-mentioned metal-containing film-forming compound and (B) an organic solvent.

[0215] <(A) Metal-containing film-forming compound>

[0216] (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, relative to a total of 100 parts by mass of components (A) and (B), it can be set to 1 to 20 parts by mass, preferably 2 to 10 parts by mass.

[0217] <(B) Organic solvent>

[0218] 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 the following (C) crosslinking agent, (D) acid generator, (E) surfactant, (B') high-boiling solvent, and other additives when contained.

[0219] Specifically, for example, an organic solvent described in paragraphs

[0091] to

[0092] of Japanese Patent Laid-Open No. 2007-199653 can be added. More specifically, it is preferable to use propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, 2-heptanone, cyclopentanone, cyclohexanone, γ-butyrolactone, or a mixture containing one or more of these.

[0220] 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).

[0221] <(B’) High-boiling solvent>

[0222] In the metal-containing film-forming composition of the present invention, the aforementioned (B) organic solvent may also contain (B’) high-boiling solvent. The (B’) high-boiling solvent can be one or more organic solvents having a boiling point of 180 degrees Celsius (°C) or higher.

[0223] For example: as the (B) organic solvent, a mixture of one or more organic solvents having a boiling point below 180°C and one or more organic solvents having a boiling point of 180°C or higher ((B’) high-boiling solvent) can be used.

[0224] (B’) The high-boiling solvent only needs to be able to dissolve each component of the metal-containing film-forming composition of the present invention, and there are no special restrictions such as hydrocarbon solvents, alcohol solvents, ketone solvents, ester solvents, ether solvents, and chlorine-based solvents. Specific examples include 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 mono-isobutyl 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 monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monopropyl 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.

[0225] (B’) The high-boiling solvent can be appropriately selected from the above in consideration of the temperature for heat-treating the metal-containing film-forming composition of the present invention. 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 fear that the volatilization during baking (heat treatment) will become too fast, so the occurrence of defects caused by drying during film formation can be suppressed. Also, if the boiling point is such, it will not remain unvolatile in the film after baking, so there is no fear of adversely affecting the film properties such as etching resistance.

[0226] Furthermore, when using the (B’) high-boiling solvent, the blending amount is preferably 1 to 30 parts by mass relative to 100 parts by mass of the organic solvent having a boiling point below 180°C. If the blending amount is such, sufficient thermal fluidity can be imparted during baking, it will not remain in the film, and it will not cause deterioration of the film properties such as etching resistance, so it is ideal.

[0227] <Other components>

[0228] The above-described metal-containing film-forming composition can be used as an underlayer film or an intermediate film of a resist used in a multilayer resist method. The metal-containing film-forming composition contains at least one kind of the above (A) metal-containing film-forming compound and (B) organic solvent, and may also contain (C) crosslinking agent, (D) acid generator, (E) surfactant, and (B') high-boiling solvent as needed.

[0229] The following describes the components other than the above (A) metal-containing film-forming compound and (B) organic solvent that can be contained in the metal-containing film-forming composition of the present invention.

[0230] [(C) Crosslinking agent]

[0231] In addition, in the metal-containing film-forming composition of the present invention, in order to improve the curability and to further suppress the cross-mixing with the upper resist film, (C) crosslinking agent may be added.

[0232] There is no particular limitation on the crosslinking agent, and various known crosslinking agents of various systems can be widely used. For example, 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 can be cited.

[0233] The above (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 (A) metal-containing film-forming compound. If the addition amount is 5 parts or more, sufficient curability will be exhibited, and cross-mixing with the upper resist film can be suppressed. On the other hand, if the addition amount is 50 parts or less, there is no fear of deterioration of dry etching resistance due to a decrease in the ratio of the (A) metal-containing film-forming compound in the composition.

[0234] Specifically, for melamine-based crosslinking agents, for example, hexamethoxymethylated melamine, hexabutoxymethylated melamine, alkoxy and / or hydroxy substituents thereof, and partial self-condensates thereof.

[0235] Specifically, for glycoluril-based crosslinking agents, for example, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, alkoxy and / or hydroxy substituents thereof, and partial self-condensates thereof.

[0236] Benzoguanamine crosslinking agents, specifically, for example, tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, alkoxy and / or hydroxy substituents thereof, and partial self-condensates thereof.

[0237] Urea crosslinking agents, specifically, for example, dimethoxymethylated dimethoxyethyleneurea, alkoxy and / or hydroxy substituents thereof, and partial self-condensates thereof.

[0238] β-Hydroxyalkylamide crosslinking agents, specifically, for example, N,N,N’,N’-tetrakis(2-hydroxyethyl)adipamide.

[0239] Isocyanurate crosslinking agents, specifically, for example, tris(2,3-epoxypropyl)isocyanurate, triallyl isocyanurate.

[0240] Aziridine crosslinking agents, specifically, for example, 4,4’-bis(ethyleneiminocarbonylamino)diphenylmethane, 2,2-bis(hydroxymethyl)butanol-tris[3-(1-aziridinyl)propionate].

[0241] Oxazoline crosslinking agents, specifically, for example, 2,2’-isopropylidenebis(4-benzyl-2-oxazoline), 2,2’-methylenebis(4,5-diphenyl-2-oxazoline), 2,2’-methylenebis(4-phenyl-2-oxazoline), 2,2’-methylenebis(4-tert-butyl-2-oxazoline), 2,2’-bis(2-oxazoline), 1,3-phenylenebis(2-oxazoline), 1,4-phenylenebis(2-oxazoline), 2-isopropenyl oxazoline copolymer.

[0242] Epoxy crosslinking agents, specifically, for example, 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.

[0243] Phenol crosslinking agents, specifically, for example, compounds represented by the following general formula (10).

[0244] [Chemical formula 20]

[0245]

[0246] 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

[0247] Q is a single bond or a q-valent hydrocarbon group having 1 to 20 carbon atoms. q 1 is an integer of 1 to 5. 1is an integer from 1 to 5, more preferably 2 or 3. Specifically, for Q, examples include 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. Specifically, examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, ethylhexyl, decyl, eicosyl, and it is preferably a hydrogen atom or a methyl group.

[0248] Examples of the compound represented by the above general formula (10) include the following compounds. Among them, from the viewpoint of improving the hardening property and film thickness uniformity of the conformal film, the hexa-methoxymethylated products of triphenylmethane, triphenylethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferred.

[0249] [Chemical formula 21]

[0250]

[0251] [Chemical formula 22]

[0252]

[0253] <(D) Acid generator>

[0254] In the metal-containing film-forming composition of the present invention, in order to further promote the hardening reaction of the above (A) metal-containing film-forming compound, a (D) acid generator can be added. Acid generators that generate acid by thermal decomposition or by light irradiation can both be added. Specifically, the materials described in paragraphs

[0061] to

[0085] of Japanese Patent Application Laid-Open No. 2007-199653 can be added, but are not limited to these.

[0255] 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, relative to 100 parts by mass of the above (A) metal-containing film-forming compound.

[0256] <(E) Surfactant>

[0257] In the metal-containing film-forming composition of the present invention, in order to improve the coatability of spin coating, a surfactant (E) can 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.

[0258] <Metal-containing film-forming method>

[0259] In the present invention, there is provided a method for forming an underlayer resist film or an intermediate film for a multilayer resist film used in lithography or a filling film serving as a planarization film for semiconductor manufacturing using the above-mentioned metal-containing film-forming composition.

[0260] 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, the solvent is evaporated, and baking (heat treatment) is performed to prevent mixing with the upper resist film and the intermediate resist film and to 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, 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 for wafer processing in lithography is preferably set to 600°C or lower, more preferably 500°C or lower.

[0261] Furthermore, in the metal-containing film-forming method using the metal-containing film-forming composition of the present invention, the metal-containing film-forming composition of the present invention can be coated on a substrate to be processed in the same manner as above by a spin coating method or the like, and the above-mentioned metal-containing film-forming composition is fired in a gas environment with an oxygen concentration of 0.1% by volume or more and 21% by volume or less to be hardened, thereby forming a metal-containing film.

[0262] By firing the metal-containing film-forming composition of the present invention in such an oxygen environment, a sufficiently hardened film can be obtained. The gas environment during baking can be air, but in order to reduce oxygen, inert gases such as N2, Ar, and He are pre-filled, which is ideal for preventing oxidation of the metal-containing film. In order to prevent oxidation, it is necessary to control the oxygen concentration, preferably 1000 ppm or less, more preferably 100 ppm or less (volume basis). Preventing oxidation of the metal-containing film during baking is ideal because it will not cause an increase in absorption or a decrease in etching resistance.

[0263] <Pattern formation method using a metal-containing film-forming composition>

[0264] Next, a pattern formation method using the metal-containing film-forming composition of the present invention will be described.

[0265] <Two-layer resist process>

[0266] The present invention provides a pattern formation method. As a pattern formation method by a two-layer resist process using the above-described metal-containing film-forming composition, it has the following steps:

[0267] (I-1) After coating the above-described metal-containing film-forming composition on a substrate to be processed, a metal-containing film is formed by heat treatment.

[0268] (I-2) A resist upper layer film is formed on the above-described metal-containing film using a photoresist material.

[0269] (I-3) After the above-described resist upper layer film is pattern-exposed, it is developed with a developer to form a pattern on the above-described resist upper layer film.

[0270] (I-4) Using the above-described patterned resist upper layer film as a mask, the pattern is transferred to the above-described metal-containing film by dry etching, and

[0271] (I-5) Using the above-described patterned metal-containing film as a mask, the above-described substrate to be processed is processed to form a pattern on the above-described substrate to be processed.

[0272] The resist upper layer film of the above two-layer resist process shows resistance to etching using a chlorine-based gas. Therefore, in the above two-layer resist process, for the dry etching of the metal-containing film using the resist upper layer film as a mask, it is preferably carried out using an etching gas mainly composed of a chlorine-based gas.

[0273] In order to ensure the adhesion to the resist upper layer film, an adhesion film may also be formed between the resist upper layer film and the metal-containing film of the present invention. The adhesion film can use an organic film or a silicon-containing film containing polysiloxane.

[0274] The pattern formation method by the resist process using the above-described metal-containing film-forming composition of the present invention is effective in improving the exposure sensitivity of the resist upper layer film. Therefore, it is preferably used as a lower layer film close to the resist upper layer film, and more preferably used directly under the resist upper layer film. When an adhesion film is used between the resist upper layer film and the metal-containing film, the film thickness of the adhesion film is preferably 20 nm or less, more preferably 15 nm or less, and still more preferably 10 nm or less. The thinner the film thickness of the adhesion film, the greater the proportion of the metal-containing film contributing to the improvement of the exposure sensitivity of the resist upper layer film, so it is ideal.

[0275] <Three-layer resist process>

[0276] Furthermore, the present invention provides a pattern forming method, which is a pattern forming method by a three-layer resist process using the metal-containing film forming composition as described above, and is characterized by having the following steps:

[0277] (II-1) Form an organic resist lower layer film on the substrate to be processed.

[0278] (II-2) After coating the metal-containing film forming composition on the organic resist lower layer film, form a metal-containing film by heat treatment.

[0279] (II-3) Form a resist upper layer film on the metal-containing film using a photoresist material.

[0280] (II-4) After pattern-exposing the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film.

[0281] (II-5) Use the patterned resist upper layer film as a mask and transfer the pattern to the metal-containing film by dry etching.

[0282] (II-6) Use the metal-containing film with the transferred pattern as a mask and transfer the pattern to the organic resist lower layer film by dry etching, and

[0283] (II-7) Use the patterned organic resist lower layer film as a mask and process the substrate to be processed to form a pattern on the substrate to be processed.

[0284] Regarding the pattern forming method by the three-layer resist process of the present invention, refer to Figure 1 Description. First, after forming an organic resist lower layer film 2 (I-A) on the substrate to be processed 1, use the metal-containing film forming composition of the present invention to form a metal-containing film 3 as a resist intermediate film (I-B), and form a resist upper layer film 4 (I-C) thereon using a photoresist material. Second, use a mask 5 to expose the resist upper layer film 4 (I-D), and perform PEB (post-exposure bake) (I-E). Second, develop to form a resist upper layer film pattern 4a (I-F). Second, use the resist upper layer film pattern 4a as a mask and perform dry etching on the metal-containing film 3 to form a metal-containing film pattern 3a (I-G). Second, after removing the resist upper layer film pattern 4a, use the metal-containing film pattern 3a as a mask and perform dry etching on the organic resist lower layer film 2 to form an organic resist lower layer film pattern 2a (I-H). After removing the metal-containing film pattern 3a, use the organic resist lower layer film pattern 2a as a mask and perform etching on the substrate to be processed 1 to form a pattern 1a (I-I).

[0285] The above-mentioned three-layer resist-treated metal-containing film shows resistance to etching with an oxygen-based gas. Therefore, in the above-mentioned three-layer resist treatment, it is preferable to use an etching gas mainly composed of an oxygen-based gas for the dry etching of the organic resist underlayer film using the metal-containing film as a mask.

[0286] As the material for the organic resist underlayer film that can be used for the above-mentioned organic resist underlayer film, those that can be used as the underlayer film for the three-layer resist method or the two-layer resist method using a silicon resist composition and are already known, the 4,4'-(9-fluorenylidene) bisphenol novolak resin (molecular weight 11,000) described in Japanese Patent Laid-Open No. 2005-128509, and various resins represented by novolak resins and already known as the resist underlayer film materials for the two-layer resist method and the three-layer resist method, etc. Also, when it is desired to further improve the heat resistance compared to the ordinary novolak resin, a polycyclic skeleton such as 6,6'-(9-fluorenylidene)-bis(2-naphthol) novolak resin can be added. In addition, a polyimide-based resin (for example, Japanese Patent Laid-Open No. 2004-153125) can also be further selected.

[0287] The above-mentioned organic resist underlayer film can use a composition solution and is formed on the substrate to be processed by a spin coating method or the like in the same manner as a photoresist composition. After forming the organic resist underlayer film by a spin coating method or the like, baking is preferably performed to evaporate the organic solvent. The baking temperature is preferably in the range of 80 to 400 °C, and the baking time is preferably in the range of 10 to 300 seconds.

[0288] The above-mentioned organic resist underlayer film material can also be replaced with an organic hard mask formed by CVD method or ALD method.

[0289] Furthermore, the present invention provides a pattern formation method, which is a pattern formation method for a three-layer resist treatment using a composition for forming a metal-containing film as described above, and is characterized by having the following steps:

[0290] Form a metal-containing film on the substrate to be processed using the above-mentioned composition for forming a metal-containing film, form 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, form a resist upper layer film using a photoresist material on the inorganic hard mask, after pattern exposure of the resist upper layer film, develop it with a developer to form a pattern in the resist upper layer film, use the resist upper layer film with the formed pattern as a mask, transfer the pattern to the inorganic hard mask intermediate film by dry etching, use the inorganic hard mask intermediate film with the transferred pattern as a mask, transfer the pattern to the metal-containing film by dry etching, and use the metal-containing film with the formed pattern as a mask to process the substrate to be processed to form a pattern on the substrate to be processed.

[0291] <4-layer resist process>

[0292] In addition, the present invention provides a pattern forming method, which is a pattern forming method using such a metal-containing film forming composition by a 4-layer resist process, and is characterized by having the following steps:

[0293] (III-1) After coating the above-mentioned metal-containing film forming composition on a substrate to be processed, a metal-containing film is formed by heat treatment.

[0294] (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 above-mentioned metal-containing film.

[0295] (III-3) An organic thin film (e.g., an organic antireflection film (BARC) or a sealing film) is formed on the above-mentioned inorganic hard mask intermediate film.

[0296] (III-4) A resist upper layer film is formed on the above-mentioned organic thin film using a photoresist material.

[0297] (III-5) After the above-mentioned resist upper layer film is pattern-exposed, it is developed with a developer to form a pattern on the above-mentioned resist upper layer film.

[0298] (III-6) Using the above-mentioned patterned resist upper layer film as a mask, the pattern is transferred to the above-mentioned organic thin film and the above-mentioned inorganic hard mask intermediate film by dry etching.

[0299] (III-7) Using the above-mentioned patterned inorganic hard mask intermediate film as a mask, the pattern is transferred to the above-mentioned metal-containing film by dry etching, and

[0300] (III-8) Using the above-mentioned patterned metal-containing film as a mask, the above-mentioned substrate to be processed is processed to form a pattern on the above-mentioned substrate to be processed.

[0301] At this time, it is preferable that the above-mentioned inorganic hard mask intermediate film is formed by CVD method or ALD method.

[0302] If the above-mentioned inorganic hard mask is formed by CVD method or ALD method, a fine pattern can be formed on the object to be processed with higher precision.

[0303] When a silicon-containing resist intermediate film is used as the inorganic hard mask intermediate film in the above-described pattern forming method, it is also preferable to use a polysiloxane-based intermediate film as the silicon-containing resist intermediate film. By providing the silicon-containing resist intermediate film with an antireflection effect, reflection can be suppressed. In particular, in the case of 193 nm exposure applications, if a material containing many aromatic groups and having a high etching selectivity with respect to the substrate is used as the organic film, the k value is high and the substrate reflection increases. However, by providing absorption that provides an appropriate k value as the silicon-containing resist intermediate film, reflection can be suppressed and the substrate reflection can be made 0.5% or less. As the silicon-containing resist intermediate film having an antireflection effect, it is preferable to use anthracene for 248 nm and 157 nm exposure applications, and a polysiloxane having a phenyl group or a light-absorbing group having a silicon-silicon bond suspended therefrom and crosslinked by an acid or heat for 193 nm exposure applications.

[0304] Regarding the inorganic hard mask intermediate film, an inorganic hard mask can also be formed. In this case, at least on the object to be processed, 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. An upper resist film is formed on the inorganic hard mask using a photoresist composition, a circuit pattern is formed in the upper resist film, the inorganic hard mask is etched using the patterned upper resist film as a mask, the metal-containing film is etched using the patterned inorganic hard mask as a mask, and the object to be processed is etched using the patterned metal-containing film as a mask to form a pattern on the object to be processed, whereby a semiconductor device circuit pattern can be formed on the substrate.

[0305] 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, regarding the method for forming a silicon nitride film, it 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. Also, for the inorganic hard mask, it is most preferable to use a SiON film having a high antireflection film effect. Since the substrate temperature during the formation of the SiON film becomes 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, so it can be a combination of an inorganic hard mask formed by a CVD method or an ALD method and a metal-containing film formed by a spin coating method.

[0306] As described above, a photoresist film may be formed on the inorganic hard mask as the upper resist film, but an organic anti-reflection film (BARC) or a conformal film may also be formed on the inorganic hard mask by spin coating, and a photoresist film may be formed thereon. In particular, when using a SiON film as the inorganic hard mask, a two-layer anti-reflection film of the SiON film and the BARC can suppress reflection even in immersion exposure with a high NA exceeding 1.0. Another advantage of forming the BARC is the effect of reducing the tailing of the photoresist pattern directly above the SiON film.

[0307] In the above-described pattern formation method, the upper resist film may be positive or negative, and the same composition as that of the commonly used photoresist composition may 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 using the above-described photoresist composition, the spin coating method or the vapor deposition method by CVD or ALD may be used.

[0308] When forming the photoresist composition by the spin coating method, pre-baking is performed after resist coating, and conditions in the range of 60 to 180 °C for 10 to 300 seconds are preferred. Thereafter, exposure is performed in the usual manner, and post-exposure baking (PEB) and development are performed to obtain a resist pattern. Further, the thickness of the upper resist film is not particularly limited, and 10 to 500 nm, particularly 20 to 400 nm, is preferred.

[0309] When forming the photoresist composition by the vapor deposition method by CVD or ALD, the photoresist composition is an EUV-sensitive metal oxide film, and the metal is selected from Sn, Zr, Hf, Ti, Bi, Sb, etc., and among them, Sn with excellent EUV sensitivity is preferred. The film containing a metal oxide may also be a photosensitive organometallic oxide film such as an organotin oxide (e.g., haloalkyl Sn, alkoxyalkyl Sn, or amidoalkyl Sn). Some specific examples of suitable precursors include trimethyltin chloride, dimethylditin dichloride, methyltin trichloride, tris(dimethylamino)methyltin(IV), and (dimethylamino)trimethyltin(IV).

[0310] Metal oxide films, for example: The Lam Vector (registered trademark) tool can be used for evaporation coating by PECVD or PEALD. In the ALD embodiment, the Sn oxide precursor can be separated from the O precursor / plasma. The evaporation coating temperature is preferably in the range of 50°C to 600°C. The evaporation coating pressure is preferably between 100 and 6000 mTorr. The flow rate of the precursor liquid containing the metal oxide film (for example: organotin oxide precursor) can be 0.01 to 10 cmm, and the gas flow rate (CO2, CO, Ar, N2) can be 100 to 10000 sccm. For plasma power, high-frequency plasma (for example: 13.56 MHz, 27.1 MHz, or higher frequency) can be used, and it is 200 to 1000 W for each 300 mm wafer station. The evaporation coating thickness is preferably 100 to 2000 Å.

[0311] The exposure light is high-energy rays with a wavelength of 300 nm or less. Specifically, for example, excimer lasers with wavelengths of 248 nm, 193 nm, and 157 nm, soft X-rays with wavelengths of 3 to 20 nm, electron beams, X-rays, etc.

[0312] As the method for forming a pattern on the upper layer film of the resist described above, optical lithography with a wavelength of 5 nm or more and 300 nm or less, direct drawing using an electron beam, nanoimprinting, or a combination of these can be used to form a pattern. However, in the present invention, EUV light is the most ideal.

[0313] Also, for the development method of the aforementioned pattern formation method, development with an alkali or development using an organic solvent is preferred.

[0314] Then, the obtained resist pattern is used as a mask for etching. For the etching of the silicon-containing resist intermediate film and the inorganic hard mask in the three-layer resist process, a fluorocarbon-based gas is used and the upper layer resist pattern is used as a mask. Thereby, a silicon-containing resist intermediate film pattern and an inorganic hard mask pattern are formed.

[0315] Next, 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. For the etching processing of the metal-containing film, it is preferably performed using an etching gas with a chlorine-based gas as the main component.

[0316] The etching of the next workpiece to be processed can also be carried out by 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 with a fluorocarbon-based gas as the main component is performed. When the substrate is etched with a fluorocarbon-based gas, the silicon-containing resist intermediate film pattern in the three-layer resist process will be peeled off simultaneously during the substrate processing.

[0317] The metal-containing film obtained using the composition for forming a metal-containing film of the present invention has the characteristic of excellent etching resistance when etching these workpieces to be processed.

[0318] Furthermore, the workpiece (workpiece substrate) is not particularly limited, and substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, and films having a processed layer formed thereon 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 and their barrier films can be used, and a thickness of usually 50 to 10,000 nm, particularly 100 to 5,000 nm can be formed. Also, when forming the processed layer, substrates and processed layers made of different materials can be used.

[0319] <Multilayer resist process>

[0320] Furthermore, the present invention provides a pattern forming method, which is a pattern forming method using a multilayer resist process with the above-described metal-containing film forming composition, and is characterized by having the following steps:

[0321] (IV-1) After coating the above-described metal-containing film forming composition on the workpiece substrate, a metal-containing film is formed by heat treatment.

[0322] (IV-2) An organic intermediate film is formed on the above-described metal-containing film.

[0323] (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 above-described organic intermediate film.

[0324] (IV-4) A resist upper layer film is formed on the above-described silicon-containing resist intermediate film or the above-described organic thin film using a photoresist material.

[0325] (IV-5) After pattern exposure of the above-described resist upper layer film, development is performed with a developer to form a pattern on the above-described resist upper layer film.

[0326] (IV-6) Using the above-described patterned resist upper layer film as a mask, the pattern is transferred to the above-described silicon-containing resist intermediate film or the above-described organic thin film and the above-described inorganic hard mask intermediate film by dry etching.

[0327] (IV-7) Using the above-described silicon-containing resist intermediate film or inorganic hard mask intermediate film onto which the pattern has been transferred as a mask, the pattern is transferred to the above-described organic intermediate film by dry etching.

[0328] (IV-8) Using the above-described organic intermediate film as a mask, the pattern is transferred to the above-described metal-containing film by dry etching, and

[0329] (IV-9) Using the aforementioned metal-containing film with a formed pattern as a mask, process the aforementioned substrate to be processed to form a pattern on the aforementioned substrate to be processed.

[0330] As an example of a pattern formation method by a multi-layer resist process using a composition for forming such a metal-containing film, for example, a pattern formation method characterized by the following steps: On a substrate to be processed, form a metal-containing film using the aforementioned composition for forming a metal-containing film, form an organic intermediate film on the metal-containing film using an organic resist underlayer film material, form a silicon-containing resist intermediate film on the organic intermediate film using a silicon-containing resist intermediate film material, optionally form an organic anti-reflective coating (BARC) or a conformal film on the silicon-containing resist intermediate film, form a resist upper layer film on the silicon-containing resist intermediate film or the BARC or the conformal film using a photoresist material, after pattern exposure of the resist upper layer film, develop with a developer to form a pattern on the resist upper layer film, use the resist upper layer film with the formed pattern as a mask, transfer the pattern to the BARC or the conformal film and the silicon-containing resist intermediate film by dry etching, use the silicon-containing resist intermediate film with the transferred pattern as a mask, transfer the pattern to the organic intermediate film by dry etching, use the organic intermediate film as a mask, transfer the pattern to the metal-containing film, use the metal-containing film with the formed pattern as a mask, and process the substrate to be processed to form a pattern on the substrate to be processed.

[0331] As the organic resist underlayer film material that can be used for the above organic intermediate film, those known as the underlayer film for the three-layer resist process or the two-layer resist process using a silicon resist composition can be used, such as the novolak resin (molecular weight 11,000) of 4,4'-(9-fluorenylidene)bisphenol described in Japanese Patent Application Laid-Open No. 2005-128509. In addition, various resins such as novolak resins can be cited, and those known as the resist underlayer film materials for the two-layer resist process and the three-layer resist process can be used. Further, when it is desired to improve the heat resistance more than that of ordinary novolak, a polycyclic skeleton such as 6,6'-(9-fluorenylidene)-bis(2-naphthol) novolak resin can be added, and a polyimide resin (for example, Japanese Patent Application Laid-Open No. 2004-153125) can also be selected.

[0332] The above organic intermediate film can be formed on the substrate to be processed by a spin coating method or the like using a composition solution, similar to a photoresist composition. After forming the organic underlayer film by a spin coating method or the like, it is preferable to perform baking to evaporate the organic solvent. The baking temperature is preferably in the range of 80 to 400 °C, and the baking time is preferably in the range of 10 to 300 seconds.

[0333] An organic hard mask formed by CVD method or ALD method can also be used instead of the above organic resist underlayer film material.

[0334] The above-mentioned organic intermediate film treated with a multilayer resist shows resistance to etching using a chlorine-based gas. Therefore, in the above-mentioned multilayer resist treatment, dry etching of a metal-containing film using the organic intermediate film as a mask is preferably performed using an etching gas mainly composed of a chlorine-based gas.

[0335] Examples

[0336] The following synthesis examples, examples, and comparative examples illustrate the present invention in more detail, but the present invention is not limited to these examples.

[0337] [Synthesis of Compounds (A-1) to (A-19) for Forming Metal-Containing Films]

[0338] In the following synthesis examples, the following organic group raw material groups G: (G1) to (G14) and silicon-containing organic group raw material groups H: (H1) to (H2) are used.

[0339] Raw material group G: (G1) to (G14) are as follows.

[0340] [Chemical Formula 23]

[0341]

[0342] Raw material group H: (H1) to (H2) are as follows.

[0343] [Chemical Formula 24]

[0344]

[0345] As the metal source M, the following metal compounds are used.

[0346] (M1): Hafnium(IV) n-butoxide

[0347] (M2): Titanium tetraisopropoxide

[0348] (M3): Zirconium(IV) tetrabutoxide (80 wt% 1-butanol solution)

[0349] [Synthesis Example 1] Synthesis of Compound (A-1) for Forming Metal-Containing Film

[0350] 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 17.6 g of compound G1 in 35.0 g of a PGMEA / PGME (weight ratio 70 / 30) solution was added to the aforementioned reaction system. The reaction temperature was maintained at 60 °C, and stirring was continued for 1 hour. After cooling to room temperature, the obtained reaction solution was filtered through a 0.45 μm PTFE filter to obtain a PGMEA / PGME solution containing the metal-containing film-forming compound (A-1). The concentration of the components other than the solvent in this solution was 24% by mass.

[0351] [Synthesis Examples 2 to 16] Synthesis of Compounds (A-2) to (A-15) and Comparative Example Compound (R-1)

[0352] Using the above metal source M and the above compound group G in the feed amounts shown in Table 1, and under the same reaction conditions as in Synthesis Example 1, compounds (A-2) to (A-15) and the comparative example compound (R-1) shown in Table 1 were obtained.

[0353] [Table 1]

[0354]

[0355]

[0356] [Synthesis Example 17] Synthesis of Metal-Containing Film-Forming Compound (A-16)

[0357] 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 14.4 g of compound G8 in 22.0 g of a PGMEA / PGME (weight ratio 70 / 30) solution was added to the aforementioned reaction system. The reaction temperature was maintained at 60 °C, and stirring was continued for 1 hour. After cooling to room temperature, the obtained reaction solution was filtered through a 0.45 μm PTFE filter to obtain a PGMEA / PGME solution containing the metal-containing film-forming compound (A-16). The concentration of the components other than the solvent in the aforementioned solution was 22% by mass.

[0358] [Synthesis Example 18] Synthesis of Compound (A-17)

[0359] 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, and under the same reaction conditions as in Synthesis Example 17, the compound (A-17) shown in Table 2 was obtained.

[0360] [Table 2]

[0361]

[0362] [Synthesis Example 19] Synthesis of Metal-Containing Film-Forming Compound (A-18)

[0363] Under a nitrogen atmosphere, 0.68 g of deionized water in 27.5 g of n-butanol was added dropwise to 20.5 g of a n-butanol solution of 23.5 g of hafnium(IV) n-butoxide (M1) with stirring over 2 hours at room temperature. 14.4 g of compound (G8) was added to the resulting solution and stirred at room temperature for 30 minutes. The solution was concentrated under reduced pressure at 30 °C and then heated to 60 °C, and heating was continued under reduced pressure until no more distillate appeared. At the point when no more distillate was seen, 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-18). The concentration of the components other than the solvent in the aforementioned solution was 21% by mass.

[0364] [Synthesis Example 20] Synthesis of Compound (A-19)

[0365] Using the above metal source M and the above compound group G at the feed rates shown in Table 3, and under the same reaction conditions as in Synthesis Example 19, the compound (A-19) shown in Table 3 was obtained.

[0366] [Table 3]

[0367]

[0368] [Preparation of Metal-Containing Film-Forming Composition]

[0369] 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]

[0370] The crosslinking agents (XL-1) to (XL-2) used in the metal-containing film-forming composition are as follows.

[0371] [Chemical Formula 25]

[0372]

[0373] [Acid Generator (D-1)]

[0374] The acid generator (D-1) used in the metal-containing film-forming composition is as follows.

[0375] [Chemical Formula 26]

[0376] (CH3CH2)3N + H

[0377] C4F9SO3 -

[0378] (D1)

[0379] [Preparation Example 1] Preparation of the metal-containing film-forming composition (UDL-1)

[0380] 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) in the ratio shown in Table 4 and filtered through a 0.02-μm membrane filter to prepare the metal-containing film-forming composition (UDL-1).

[0381] [Preparation Examples 2 to 23] Preparation of the metal-containing film-forming compositions (UDL-2 to 22) and the metal-containing film-forming composition for comparative example (Comparative Example UDL-1)

[0382] The type and content of each component were changed as shown in Table 4, and the same operations as those for UDL-1 were performed except for this to prepare each liquid medicine. Also, in Table 4, "-" represents that the corresponding component was not used. The high-boiling solvent (F-1) used was ethylene glycol dibenzyl ether: boiling point 364°C.

[0383] [Table 4]

[0384]

[0385]

[0386] [Examples 1-1 to 1-22, Comparative Example 1-1]

[0387] [Patterning Test]

[0388] 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 22 and Comparative Example UDL-1 were spin-coated on the aforementioned Si substrate and heated at 250°C for 60 seconds to form a metal-containing film with a film thickness of 20 nm.

[0389] Next, a photoresist material in which the following components are dissolved in the ratio of Table 5 was spin-coated on a metal-containing film and prebaked at 105 °C for 60 seconds using a hot plate to form a resist film with a thickness of 60 nm. It was exposed using an EUV scanning exposure machine NXE3300 manufactured by ASML (NA 0.33, σ 0.9 / 0.6, quadrupole illumination, mask with a hole pattern having a pitch of 46 nm and a +20% deviation in size on the wafer), PEB was performed at 100 °C for 60 seconds on a hot plate, and development was carried out for 30 seconds with a 2.38 mass% aqueous TMAH solution to obtain a hole pattern with a size of 23 nm.

[0390] The exposure dose when the hole size was formed to 23 nm was measured using a length-measuring SEM (CG5000) manufactured by Hitachi High-Technologies Corporation, and this was defined as the sensitivity. Also, the sizes of 50 holes at this time were measured, and the size variation (CDU, 3σ) was determined. The results are shown in Table 6.

[0391] [Chemical formula 27]

[0392]

[0393] [Chemical formula 28]

[0394]

[0395] Surfactant: FC-4430 manufactured by 3M

[0396] [Table 5]

[0397]

[0398] · Organic solvent: PGMEA (propylene glycol monomethyl ether acetate) CyHO (cyclohexanone)

[0399] PGME (propylene glycol monomethyl ether)

[0400] [Table 6]

[0401]

[0402] From the results shown in Table 6, it can be seen that if a metal-containing film having a ligand substituted with a halogen atom selected from among chlorine atoms, bromine atoms, and iodine atoms formed using a metal-containing film-forming composition containing the metal-containing film-forming compound of the present invention is used as an antireflective intermediate film, a pattern can be formed with high sensitivity without deterioration of CDU (Examples 1-1 to 1-22). From this, it can be understood that the above antireflective intermediate film can maintain the LWR of the upper resist and contribute to an improvement in sensitivity.

[0403] When fixing metal atoms with hafnium and comparing the effects of ligands on the sensitivity of the upper layer of the resist, the sensitivity of the examples using metal compounds containing iodine atoms among chlorine atoms, bromine atoms, and iodine atoms was good. Moreover, the sensitivity of the examples using metal compounds containing an aromatic ring substituted with an iodine atom as a ligand was even better (Examples 1-3 and 1-8), and the sensitivity of the examples using metal compounds containing an aromatic ring substituted with an organic group containing an iodine atom and a crosslinking group as a ligand was even better (Example 1-11). It is speculated that since it contains not only metal atoms with large light absorption but also iodine atoms with large light absorption, and contains an aromatic ring substituted with an organic group containing a crosslinking group, a metal-containing film with excellent heat resistance can be formed, and the sensitization effect caused by secondary electrons generated during exposure in EUV lithography is better.

[0404] On the other hand, when using a resist intermediate film formed from a metal-containing film-forming composition using a metal-containing film-forming compound that does not contain any chlorine atoms, bromine atoms, or iodine atoms in the ligand, a result with poor sensitivity was obtained (Comparative Example 1-1).

[0405] As described above, the present invention breaks the trade-off relationship between sensitivity and LWR, and can form a resist lower layer film or intermediate film that maintains the LWR of the upper resist and helps to improve sensitivity. Therefore, it has high utility value in the field of EUV lithography.

[0406] Moreover, the present invention is not limited to the above embodiments. The above embodiments are illustrative, and those having substantially the same constitution and exhibiting the same effects as the technical idea described in the claims of the present invention are all included in the technical scope of the present invention.

[0407] This specification includes the following inventions.

[0408] [1]: A metal-containing film-forming compound, characterized in that:

[0409] The aforementioned 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 aforementioned metal atom (a).

[0410] And the aforementioned multidentate ligand is derived from a compound (b) having 1 to 50 carbon atoms substituted with at least one halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom.

[0411] [2]: The metal-containing film-forming compound according to [1], wherein the aforementioned compound (b) contains any of the structures represented by the following general formulas (b-1) to (b-4).

[0412] [Chemical formula 29]

[0413]

[0414] 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 any one of a chlorine atom, a bromine atom, and an iodine atom, R4 to R5 are hydrogen atoms or monovalent organic groups having 1 to 30 carbon atoms which may also contain any one of a chlorine atom, a bromine atom, and an iodine atom, R6 to R9 are hydrogen atoms or monovalent organic groups having 1 to 30 carbon atoms which may also contain any one of a chlorine atom, a bromine atom, and an iodine atom, and Y is a divalent organic group having 1 to 10 carbon atoms. 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 formulas (b-1) to (b-4) contain at least one or more of a chlorine atom, a bromine atom, and an iodine atom.

[0415] [3]: A metal-containing film-forming compound as in [2], wherein the compound represented by the above general formulas (b-1) to (b-4) contains at least one or more of an aromatic ring, a heteroaromatic ring, and an alicyclic structure.

[0416] [4]: A metal-containing film-forming compound as in [2] or [3], wherein the compound represented by the above general formulas (b-1) to (b-4) contains the structure represented by the following formula (1),

[0417] [Chemical formula 30]

[0418]

[0419] In the above formula, X m1 is any one of a chlorine atom, a bromine atom, and an iodine atom, or a monovalent organic group having 1 to 10 carbon atoms which contains any one of a chlorine atom, a bromine atom, and an iodine atom, W is an organic group having 5 to 20 carbon atoms which contains 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 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a halogen atom, and a halogenated alkyl group having 1 to 10 carbon atoms, s is 1 to 5, and n1 is 0 to 2.

[0420] [5]: A metal-containing film-forming compound as in any one of [1] to [4], wherein the metal-containing film-forming compound further contains a ligand (c) derived from a silicon compound represented by the following general formula (2),

[0421] [Chemical formula 31]

[0422]

[0423] In the above general formula (2), R 3A , R 3B and R 3CIt is any 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 is selected from any crosslinking group having a structure represented by the following general formulas (c-1) to (c-3).

[0424] [Chemical formula 32]

[0425]

[0426] 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.

[0427] [6]: A metal-containing film-forming compound according to any one of [1] to [5], wherein

[0428] The aforementioned metal-containing film-forming compound further contains a ligand having one or more crosslinkable groups selected from vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, and oxetanyl.

[0429] [7]: A metal-containing film-forming compound according to any one of [1] to [6], wherein the aforementioned compound (b) further has one or more crosslinkable groups selected from vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, and oxetanyl.

[0430] [8]: A metal-containing film-forming compound according to [2], wherein the aforementioned metal-containing film-forming compound is a reaction product of one or more metal compounds selected from the metal compounds represented by the following formula (3), and the hydrolyzates, condensates, and hydrolytic condensates of the metal compounds represented by the following formula (3) with any one of the compounds represented by the aforementioned formulas (b-1) to (b-4).

[0431] [Chemical formula 33]

[0432] L a MX b (3) In the formula, M is any of Ti, Zr, and Hf. L is any of monodentate ligands and polydentate ligands having 1 to 30 carbon atoms, and X is a hydrolyzable group selected from halogen atoms, alkoxy groups, carboxyl groups, acyloxy groups, -NR a R b among others. 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.

[0433] [9]: A metal-containing film-forming compound according to any one of [1] to [8], wherein the compound (b) contains one or more chlorine atoms.

[0434]

[10] : A metal-containing film-forming compound according to any one of [1] to [9], wherein the compound (b) contains one or more bromine atoms.

[0435]

[11] : A metal-containing film-forming compound according to any one of [1] to

[10] , wherein the compound (b) contains one or more iodine atoms.

[0436]

[12] : A metal-containing film-forming composition

[0437] which is 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:

[0438] (A) A metal-containing film-forming compound according to any one of [1] to

[11] , and

[0439] (B) An organic solvent.

[0440]

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

[12] , wherein

[0441] the composition further contains one or more of (C) a crosslinking agent, (D) an acid generator, and (E) a surfactant.

[0442]

[14] : The metal-containing film-forming composition according to

[12] or

[13] , wherein

[0443] the organic solvent (B) is a mixture of one or more organic solvents having a boiling point below 180°C and one or more organic solvents having a boiling point of 180°C or higher ((B') a high-boiling solvent).

[0444]

[15] : A patterning method, which is a method of forming a pattern on a substrate to be processed, and is characterized by having the following steps:

[0445] (I-1) After coating a metal-containing film-forming composition according to any one of

[12] to

[14] on the substrate to be processed, a metal-containing film is formed by heat treatment,

[0446] (I-2) A resist upper layer film is formed on the metal-containing film using a photoresist material,

[0447] (I-3) After pattern exposure of the resist upper layer film, development is carried out with a developer to form a pattern on the resist upper layer film,

[0448] (I-4) Using the above-mentioned resist upper layer film with the formed pattern as a mask, transfer the pattern to the above-mentioned metal-containing film by dry etching, and

[0449] (I-5) Using the above-mentioned metal-containing film with the formed pattern as a mask, process the above-mentioned substrate to be processed to form a pattern on the above-mentioned substrate to be processed.

[0450]

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

[0451] (II-1) Form an organic resist lower layer film on the substrate to be processed,

[0452] (II-2) After coating the composition for forming a metal-containing film according to any one of

[12] to

[14] on the above-mentioned organic resist lower layer film, form a metal-containing film by heat treatment,

[0453] (II-3) Use a photoresist material to form a resist upper layer film on the above-mentioned metal-containing film,

[0454] (II-4) After pattern exposure of the above-mentioned resist upper layer film, develop it with a developer to form a pattern on the above-mentioned resist upper layer film,

[0455] (II-5) Using the above-mentioned resist upper layer film with the formed pattern as a mask, transfer the pattern to the above-mentioned metal-containing film by dry etching,

[0456] (II-6) Using the above-mentioned metal-containing film with the transferred pattern as a mask, transfer the pattern to the above-mentioned organic resist lower layer film by dry etching, and

[0457] (II-7) Using the above-mentioned organic resist lower layer film with the formed pattern as a mask, process the above-mentioned substrate to be processed to form a pattern on the above-mentioned substrate to be processed.

[0458]

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

[0459] (III-1) After coating the composition for forming a metal-containing film according to any one of

[12] to

[14] on the substrate to be processed, form a metal-containing film by heat treatment,

[0460] (III-2) Form 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 above-mentioned metal-containing film,

[0461] (III-3) Form an organic thin film on the above-mentioned inorganic hard mask intermediate film,

[0462] (III-4) A resist upper layer film is formed on the aforementioned organic thin film using a photoresist material.

[0463] (III-5) After pattern exposure of the aforementioned resist upper layer film, it is developed with a developer to form a pattern on the aforementioned resist upper layer film.

[0464] (III-6) Using the aforementioned patterned resist upper layer film as a mask, the pattern is transferred to the intermediate film between the aforementioned organic thin film and the aforementioned inorganic hard mask by dry etching.

[0465] (III-7) Using the aforementioned inorganic hard mask intermediate film with the transferred pattern as a mask, the pattern is transferred to the aforementioned metal-containing film by dry etching, and

[0466] (III-8) Using the aforementioned patterned metal-containing film as a mask, the aforementioned substrate to be processed is processed to form a pattern on the aforementioned substrate to be processed.

[0467]

[18] : A pattern forming method, which is a method of forming a pattern on a substrate to be processed, characterized by having the following steps:

[0468] (IV-1) On the substrate to be processed, after coating the composition for forming a metal-containing film according to any one of

[12] to

[14] , a metal-containing film is formed by heat treatment.

[0469] (IV-2) An organic intermediate film is formed on the aforementioned metal-containing film.

[0470] (IV-3) On the aforementioned organic intermediate film, a combination of a silicon-containing resist intermediate film, or 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.

[0471] (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.

[0472] (IV-5) After pattern exposure of the aforementioned resist upper layer film, it is developed with a developer to form a pattern on the aforementioned resist upper layer film.

[0473] (IV-6) Using the aforementioned patterned resist upper layer film 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.

[0474] (IV-7) Using the aforementioned silicon-containing resist intermediate film or inorganic hard mask intermediate film with the transferred pattern as a mask, the pattern is transferred to the aforementioned organic intermediate film by dry etching.

[0475] (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

[0476] (IV-9) Use the previously formed metal-containing film as a mask to process the substrate to be processed and form a pattern on the substrate to be processed.

[0477]

[19] : The pattern forming method as in

[15] , wherein in the aforementioned step (I-3), EUV light is used for the aforementioned pattern exposure.

[0478]

[20] : The pattern forming method as in

[16] , wherein in the aforementioned step (II-4), EUV light is used for the aforementioned pattern exposure.

[0479]

[21] : The pattern forming method as in

[17] , wherein in the aforementioned step (III-5), EUV light is used for the aforementioned pattern exposure.

[0480]

[22] : The pattern forming method as in

[18] , wherein in the aforementioned step (IV-5), EUV light is used for the aforementioned pattern exposure.

[0481] Furthermore, the present invention is not limited to the above embodiments. The above embodiments are illustrative, and those having substantially the same constitution and exhibiting the same effects as the technical idea described in the claims of the present invention are all included within the technical scope of the present invention.

[0482] Explanation of Reference Numerals

[0483] 1: Substrate to be processed

[0484] 1a: Pattern

[0485] 2: Organic resist underlayer film

[0486] 2a: Organic resist underlayer film pattern

[0487] 3: Metal-containing film

[0488] 3a: Metal-containing film pattern

[0489] 4: Resist upper layer film

[0490] 4a: Resist upper layer film pattern

[0491] 5: Mask

[0492] 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). The polydentate ligand is derived from a compound (b) having 1 to 50 carbon atoms substituted with at least one halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom.

2. The metal-containing film-forming compound according to claim 1, wherein The compound (b) contains any of the structures represented by the following general formulae (b-1) to (b-4), In the above general formula, R1~R3 ​​are hydrogen atoms, or monovalent organic groups with 1 to 30 carbon atoms, which may also contain any of chlorine atoms, bromine atoms, and iodine atoms; R4~R5 are hydrogen atoms, or monovalent organic groups with 1 to 30 carbon atoms, which may also contain any of chlorine atoms, bromine atoms, and iodine atoms; R6~R9 are hydrogen atoms, or monovalent organic groups with 1 to 30 carbon atoms, which may also contain any of chlorine atoms, bromine atoms, and iodine atoms; Y is a divalent organic group with 1 to 10 carbon atoms; 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 formulas (b-1) to (b-4) contain at least one of chlorine atoms, bromine atoms, and iodine atoms.

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 the above formula, X m1 is any of a chlorine atom, a bromine atom, and an iodine atom, or a monovalent organic group having 1 to 10 carbon atoms containing any of a chlorine atom, a bromine atom, and an iodine atom, W is an organic group having 5 to 20 carbon atoms containing any 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 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a halogen atom, and a halogenated alkyl group having 1 to 10 carbon atoms; s is 1 to 5, and n1 is 0 to 2.

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 above general formula (2), R 3A , R 3B and R 3C , is any organic group having 1 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or an aryl group having 1 to 20 carbon atoms, which is selected from any crosslinking group having a structure represented by the following general formulae (c-1) to (c-3), In the above 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 1, wherein The metal-containing film-forming compound further contains a ligand having 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 propargyloxy group, an epoxy group, and an oxetanyl group.

7. The metal-containing film-forming compound according to claim 6, wherein The compound (b) further has one or more crosslinking groups selected from the group consisting of vinyl, allyl, allyloxy, ethynyl, propargyl, propargyloxy, epoxy, and oxetanyl.

8. 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 polydentate ligand having 1 to 30 carbon atoms, and X is selected from a halogen atom, an alkoxy group, a carboxylic acid group, an acyloxy group, -NR a R b The hydrolyzable group in a and R b Each independently represents 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.

9. The metal-containing film-forming compound according to claim 1, wherein The compound (b) contains one or more chlorine atoms.

10. The metal-containing film-forming compound according to claim 1, wherein The compound (b) contains one or more bromine atoms.

11. The metal-containing film-forming compound according to claim 1, wherein The compound (b) contains one or more iodine atoms.

12. A metal-containing film-forming composition, A metal-containing film-forming composition serving as a resist underlayer film material or a resist intermediate film material used in semiconductor manufacturing, characterized in that contain: (A) the metal-containing film-forming compound according to any one of claims 1 to 11, and (B) Organic solvent.

13. The metal-containing film-forming composition according to claim 12, wherein The composition further contains one or more of (C) a crosslinking agent, (D) an acid generator, and (E) a surfactant.

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

15. A method for forming a pattern on a processed substrate, characterized by comprising the following steps: (I-1) After applying the metal-containing film-forming composition according to claim 12 on a substrate to be processed, a metal-containing film is formed by heat treatment, (I-2) forming a resist upper layer film on the metal-containing film using a photoresist material, (I-3) exposing the resist upper layer film to pattern exposure, and then developing the film with a developer to form a pattern on the resist upper layer film, (I-4) using the patterned resist upper layer film as a mask, transferring the pattern to the metal-containing film by dry etching, and (I-5) The substrate to be processed is processed using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

16. A method for forming a pattern on a processed substrate, The method is characterized by having the following steps: (II-1) forming an organic resist underlayer film on a substrate to be processed, (II-2) coating the organic resist underlayer film After the metal-containing film-forming composition according to claim 12, a metal-containing film is formed by heat treatment, (II-3) forming a resist upper layer film on the metal-containing film using a photoresist material, (II-4) exposing the resist upper layer film to pattern exposure, and then developing with a developer to form a pattern on the resist upper layer film, (II-5) using the patterned resist upper layer film as a mask, transferring the pattern to the metal-containing film by dry etching, (II-6) using the metal-containing film to which the pattern has been transferred as a mask, transferring the pattern to the organic resist underlayer film by dry etching, and (II-7) The substrate to be processed is processed using the patterned organic resist underlayer film as a mask to form a pattern on the substrate to be processed.

17. A method for forming a pattern on a processed substrate, characterized by comprising the following steps: (III-1) After applying the metal-containing film-forming composition according to claim 12 on a substrate to be processed, a metal-containing film is formed by 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) exposing the resist upper layer film to pattern exposure, and then developing with a developer to form a pattern on the resist upper layer film, (III-6) using the patterned resist upper layer film as a mask, 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 to which the pattern has been transferred 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 patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

18. A method for forming a pattern on a processed substrate, characterized by comprising the following steps: (IV-1) After applying the metal-containing film-forming composition according to claim 12 on a substrate to be processed, a metal-containing film is formed by heat treatment, (IV-2) forming an organic intermediate film on the metal-containing film, (IV-3) forming a 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 oxide nitride film and an organic thin film on the organic intermediate film, (IV-4) forming a resist upper layer 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 with a developer to form a pattern on the resist upper layer film, (IV-6) using the patterned resist upper film as a mask, 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 the silicon-containing resist interlayer or inorganic hard mask interlayer to which the pattern has been 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 to transfer a pattern to the metal-containing film by dry etching, and (IV-9) The substrate to be processed is processed using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

19. The pattern forming method according to claim 15, wherein: In the step (I-3), EUV light is used for pattern exposure.

20. The pattern forming method according to claim 16, wherein: In the step (II-4), the pattern exposure is performed using EUV light.

21. The pattern forming method according to claim 17, wherein: In the step (III-5), the pattern exposure is performed using EUV light.

22. The pattern forming method according to claim 18, wherein: In the step (IV-5), the pattern exposure is performed using EUV light.

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