Compound for forming metal-containing film, composition for forming metal-containing film, and patterning process

Abstract

To provide a compound for forming a metal-containing film to be used for forming a metal-containing film that can contribute to the improvement of sensitivity while maintaining the LWR of an upper layer resist; a composition for forming a metal-containing film, containing the compound; and a patterning process using the composition.SOLUTION: The present invention provides a compound for forming a metal-containing film, containing: at least one metal atom (a) selected from the group consisting of Ti, Zr, and Hf; and a ligand coordinated to the metal atom (a), where the ligand is derived from a compound (b) having 1 to 50 carbon atoms, being substituted with a halogen atom, containing a carboxy group, and containing one or more crosslinkable groups selected from a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyloxy group, an epoxy group, an oxetanyl group, and a nitrile group.SELECTED DRAWING: Figure 1

Description

Technical Field

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

Background Art

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

[0003] For the next lithography at the 7 nm node and 5 nm node, problems such as high cost due to multiple exposures and overlay accuracy problems in multiple exposures have become apparent, and the advent of EUV lithography capable of reducing the number of exposures has been expected.

[0004] Extreme ultraviolet light (EUV) with a wavelength of 13.5 nm has a wavelength that is 1 / 10 or less shorter than that of an ArF excimer laser with a wavelength of 193 nm. Therefore, EUV lithography is expected to have high contrast and high resolution of light. Since EUV has a short wavelength and a high energy density, an acid generator is sensitized by a small amount of photons. The number of photons in EUV exposure is said to be 1 / 14 of that in ArF exposure. In EUV exposure, a phenomenon in which line width roughness (LWR) and critical dimension uniformity (CDU) of holes deteriorate due to photon variation has been regarded as a problem (Non-Patent Document 1). Furthermore, the possibility of uneven distribution and aggregation of the base polymer and the acid generator, and the influence of acid diffusion generated from the acid generator have also been pointed out.

[0005] As a countermeasure, for example, it is possible to reduce LWR by lowering the post-exposure bake (PEB) temperature, but the sensitivity of the EUV resist will decrease. Furthermore, increasing the amount of quencher added also reduces LWR, but this method also results in a decrease in sensitivity. In order to put EUV resist into practical use, it is necessary to break the trade-off relationship between sensitivity and LWR.

Prior Art Documents

Non-Patent Documents

[0006]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] In order for EUV lithography to be put into practical use as a mass production process for semiconductor devices, many problems need to be solved. Among them, the characteristic that particularly requires improvement is to increase the sensitivity while maintaining LWR.

[0008] The present invention has been made in view of the above circumstances, and an object thereof is to provide a compound for forming a metal-containing film that can contribute to improving the sensitivity while maintaining the LWR of the upper-layer resist, a composition for forming a metal-containing film containing the same, and a pattern forming method using this composition.

Means for Solving the Problems

[0009] In order to solve the above problems, in the present invention, A compound for forming a metal-containing film, 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 ligand coordinated to the metal atom (a), and The ligand is a compound (b) having 1 to 50 carbon atoms which is substituted with a halogen atom, contains a carboxy group, and contains one or more crosslinkable groups selected from a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyloxy group, an epoxy group, an oxetanyl group, and a nitrile group, and provides a compound for forming a metal-containing film derived therefrom.

[0010] With such a compound for forming a metal-containing film, a composition for forming a resist underlayer film or an intermediate film that can contribute to improving the sensitivity while maintaining the LWR of the upper-layer resist can be obtained.

[0011] Further, it is preferable that the ligand is derived from a compound represented by the following formula (1).

Chemical formula

[0012] With such a compound for forming a metal-containing film, a composition for forming a resist underlayer film or an intermediate film that can contribute to improving the sensitivity while maintaining the LWR of the upper-layer resist can be obtained.

[0013] At this time, it is preferable that the compound represented by the general formula (1) contains at least one or more of an aromatic ring, a heteroaromatic ring, and an alicyclic structure.

[0014] With such a compound for forming a metal-containing film, since it has excellent heat resistance, the amount of sublimates during the formation of the metal oxide film can be reduced, and a metal oxide film containing many halogen atoms can be formed.

[0015] Further, R in the general formula (1) aPreferably, it has a structure represented by the following formula (1-A). [Chemical formula] (In the above formula, X1 is a halogen atom or a monovalent organic group having 1 to 10 carbon atoms containing a halogen 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 x is a monovalent organic group having 2 to 20 carbon atoms containing a crosslinkable group selected from a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyloxy group, an epoxy group, an oxetanyl group, and a nitrile group, 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, and a hydroxyl group, n1 is 1 to 5, n2 is 1 to 4, n3 is 0 to 2, and * is the bonding part with X m1 .)

[0016] For such a compound for forming a metal-containing film, since it has 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 halogen atoms can be formed.

[0017] Also, it is preferable that X m1 in the general formula (1) contains one or more carbonyl groups.

[0018] For such a compound for forming a metal-containing film, since it has 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 halogen atoms can be formed.

[0019] Also, it is preferable that the compound for forming a metal-containing film further contains a ligand (c) derived from a silicon compound represented by the following general formula (2). [Chemical formula] (In the above general formula (2), R 3A , R 3B and R 3CIt is any one of an organic group having 1 to 30 carbon atoms and having a crosslinking group of any of 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. )

Chemical formula

[0020] For such a compound for forming a metal-containing film, it becomes a compound for forming a metal-containing film excellent in stability, and the storage life stability of the composition for forming a resist underlayer film can be improved.

[0021] Further, it is preferable that the compound for forming a metal-containing film is a reaction product of a metal-containing compound containing at least one selected from a metal compound represented by the following formula (3), and a hydrolyzate, condensate, and hydrolyzate condensate of the metal compound represented by the following formula (3), and the compound represented by the formula (1).

Chemical formula

[0022] By using such a metal compound, a metal-containing film having excellent dry etching resistance against fluorine gas and oxygen gas can be formed.

[0023] Further, it is preferable that the compound represented by the general formula (1) contains one or more fluorine atoms.

[0024] For such a compound for forming a metal-containing film, a composition for forming a resist underlayer film or an intermediate film that can contribute to improving the sensitivity while maintaining the LWR of the upper-layer resist can be obtained.

[0025] In addition, it is preferable that the compound represented by the general formula (1) contains one or more chlorine atoms.

[0026] For such a compound for forming a metal-containing film, a composition for forming a resist underlayer film or an intermediate film that can contribute to improving the sensitivity while maintaining the LWR of the upper-layer resist can be obtained.

[0027] In addition, it is preferable that the compound represented by the general formula (1) contains one or more bromine atoms.

[0028] For such a compound for forming a metal-containing film, a composition for forming a resist underlayer film or an intermediate film that can contribute to improving the sensitivity while maintaining the LWR of the upper-layer resist can be obtained.

[0029] In addition, it is preferable that the compound represented by the general formula (1) contains one or more iodine atoms.

[0030] For such a compound for forming a metal-containing film, a composition for forming a resist underlayer film or an intermediate film that can contribute to improving the sensitivity while maintaining the LWR of the upper-layer resist can be obtained.

[0031] In addition, in the present invention, A composition for forming a metal-containing film that functions as a resist underlayer film material or a resist intermediate film material used in semiconductor manufacturing, (A) The above compound for forming a metal-containing film, and (B) An organic solvent A composition for forming a metal-containing film containing the same is provided.

[0032] With such a composition for forming a metal-containing film, it is possible to form a resist underlayer film or intermediate film that can contribute to an improvement in sensitivity while maintaining the LWR of the upper-layer resist.

[0033] Further, it is preferable that the composition further contains one or more of (C) a crosslinking agent, (D) an acid generator, and (E) a surfactant.

[0034] With a composition for forming a metal-containing film containing the above additives, it becomes a composition for forming a metal-containing film that is excellent in coatability, dry etching resistance, and embedding and / or planarization characteristics.

[0035] Further, it is preferable that 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 solvent).

[0036] By imparting fluidity to the above compound for forming a metal-containing film by adding a high-boiling solvent, it is possible to suppress the occurrence of coating defects due to drying of the composition for forming a metal-containing film.

[0037] Also, in the present invention, A method for forming a pattern on a substrate to be processed, comprising: (I-1) A step of forming a metal-containing film by applying the above composition for forming a metal-containing film on a substrate to be processed and then performing heat treatment; (I-2) A step of forming a resist upper-layer film on the metal-containing film using a photoresist material; (I-3) A step of forming a pattern on the resist upper-layer film by pattern exposure and then developing with a developer; (I-4) A step of transferring the pattern to the metal-containing film by dry etching using the resist upper-layer film on which the pattern is formed as a mask, and (I-5) A step of processing the substrate to be processed using the metal-containing film on which the pattern is formed as a mask to form a pattern on the substrate to be processed A pattern forming method having is provided.

[0038] By the pattern formation method using the above two-layer resist process, a fine pattern can be formed on a workpiece (workpiece substrate).

[0039] Also, in the present invention, A method for forming a pattern on a workpiece substrate, comprising: (II-1) A step of forming an organic resist lower layer film on the workpiece substrate; (II-2) A step of forming a metal-containing film by applying the above composition for forming a metal-containing film on the organic resist lower layer film and then performing heat treatment; (II-3) A step of forming a resist upper layer film on the metal-containing film using a photoresist material; (II-4) A step of forming a pattern in the resist upper layer film by performing pattern exposure on the resist upper layer film and then developing with a developer; (II-5) A step of transferring the pattern to the metal-containing film by dry etching using the resist upper layer film having the pattern as a mask; (II-6) A step of transferring the pattern to the organic resist lower layer film by dry etching using the metal-containing film having the pattern transferred thereto as a mask, and (II-7) A step of processing the workpiece substrate using the organic resist lower layer film having the pattern formed thereon as a mask to form a pattern on the workpiece substrate A pattern formation method having the above steps is provided.

[0040] By the pattern formation method using the above three-layer resist process, a fine pattern can be formed on a workpiece with high precision.

[0041] Also, in the present invention, A method for forming a pattern on a workpiece substrate, comprising: (III-1) A step of forming a metal-containing film by applying the above composition for forming a metal-containing film on the workpiece substrate and then performing heat treatment; (III-2) A step of forming an inorganic hard mask intermediate film selected from a silicon-containing resist intermediate film, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film; (III-3) Forming an organic thin film on the inorganic hard mask intermediate film; (III-4) Forming a resist upper layer film using a photoresist material on the organic thin film; (III-5) After pattern-exposing the resist upper layer film, developing it with a developer to form a pattern in the resist upper layer film; (III-6) Using the resist upper layer film with the pattern formed thereon 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 with the pattern transferred thereto as a mask, transferring the pattern to the metal-containing film by dry etching, and (III-8) Using the metal-containing film with the pattern formed thereon as a mask to process the substrate to be processed and form a pattern on the substrate to be processed A pattern forming method is provided.

[0042] By the pattern forming method using the above four-layer resist process, a fine pattern can be formed on the object to be processed with high precision.

[0043] Also, in the present invention, A method for forming a pattern on a substrate to be processed, comprising: (IV-1) Forming a metal-containing film by applying the above composition for forming a metal-containing film on the substrate to be processed and then performing a heat treatment; (IV-2) Forming an organic intermediate film on the metal-containing film; (IV-3) Forming 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 on the organic intermediate film; (IV-4) Forming a resist upper layer film using a photoresist material on the silicon-containing resist intermediate film or the organic thin film; (IV-5) After pattern-exposing the resist upper layer film, developing it with a developer to form a pattern in the resist upper layer film; (IV-6) Using the resist upper layer film on which the pattern is formed as a mask, transferring the pattern to the silicon-containing resist intermediate film, the organic thin film, and the inorganic hard mask intermediate film by dry etching; (IV-7) Using the silicon-containing resist intermediate film or the inorganic hard mask intermediate film on which the pattern is transferred as a mask, transferring the pattern to the organic intermediate film by dry etching; (IV-8) Using the organic intermediate film as a mask, transferring the pattern to the metal-containing film by dry etching, and (IV-9) Using the metal-containing film on which the pattern is formed as a mask to process the substrate to be processed and forming a pattern on the substrate to be processed provided is a pattern formation method having the above.

[0044] By the pattern formation method using the above multilayer resist process, a fine pattern can be formed on the workpiece with high precision.

[0045] Also, in the step (I-3), it is preferable to perform the pattern exposure using EUV light.

[0046] Also, in the step (II-4), it is preferable to perform the pattern exposure using EUV light.

[0047] Also, in the step (III-5), it is preferable to perform the pattern exposure using EUV light.

[0048] Also, in the step (IV-5), it is preferable to perform the pattern exposure using EUV light.

[0049] Since the compound for forming a metal-containing film of the present invention contains a halogen atom with a large light absorption, in EUV lithography, it is possible to form a resist lower layer film or an intermediate film that can contribute to improving the sensitivity while maintaining the LWR of the upper layer resist.

Effect of the Invention

[0050] The compound for forming a metal-containing film of the present invention contains a halogen atom with high light absorption in addition to a metal atom with high light absorption, so it has the characteristic that an intensifying effect by secondary electrons generated during exposure in EUV lithography can be expected.

[0051] Furthermore, since the metal-containing film obtained in the present invention has high etching selectivity with respect to an organic material, the formed photoresist pattern can be transferred to the metal-containing film, the organic underlayer film, or the CVD organic hard mask in order by using a dry etching process. In particular, in the semiconductor device manufacturing process in recent years where miniaturization has advanced, the film thickness of the photoresist film tends to be reduced in order to prevent pattern collapse after development, making it difficult to transfer the pattern to the resist underlayer film. However, when the composition for forming a metal-containing film of the present invention is used, even if 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 accuracy.

Brief Description of the Drawings

[0052]

Figure 1

Embodiments for Carrying Out the Invention

[0053] As described above, there has been a demand for the development of a compound for forming a metal-containing film, a composition for forming a metal-containing film containing the same, and a pattern forming method using this composition, which can contribute to improving the sensitivity while maintaining the LWR of the upper resist.

[0054] As a result of intensive studies to achieve the above object, the present inventors have found that by introducing a halogen atom and a crosslinkable group into the compound for forming a metal-containing film, it is possible to improve the sensitivity without deteriorating the LWR of the upper resist, and thus completed the present invention.

[0055] That is, the present invention relates to a compound for forming a metal-containing film, wherein 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 ligand coordinated to the metal atom (a), and the ligand is substituted with a halogen atom, contains a carboxy group, and is derived from a compound (b) having 1 to 50 carbon atoms and containing one or more crosslinkable groups selected from a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyloxy group, an epoxy group, an oxetanyl group, and a nitrile group.

[0056] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0057] <Compound for forming a metal-containing film> The compound for forming a metal-containing film of the present invention contains at least one metal atom (a) selected from the group consisting of Ti, Zr, and Hf, and a ligand coordinated to the metal atom (a), and the ligand is substituted with a halogen atom, contains a carboxy group, and is derived from a compound (b) having 1 to 50 carbon atoms and containing one or more crosslinkable groups selected from a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyloxy group, an epoxy group, an oxetanyl group, and a nitrile group.

[0058] The compound for forming a metal-containing film of the present invention is characterized in that the following constitution is included in the compound for forming a metal-containing film. (a) At least one metal atom selected from the group consisting of Ti, Zr, and Hf. (b) A ligand substituted with a halogen atom, containing a carboxy group, and derived from a compound (b) having 1 to 50 carbon atoms and containing one or more crosslinkable groups selected from a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyloxy group, an epoxy group, an oxetanyl group, and a nitrile group.

[0059] The metal atom contained in the compound for forming a metal-containing film is at least one metal atom selected from the group consisting of Ti, Zr, and Hf. From the viewpoint of productivity, it contains any one of Ti, Zr, and Hf, and from the viewpoints of productivity and improvement of resist sensitivity, it preferably contains either Ti or Hf.

[0060] The ligand coordinating to the compound for forming a metal-containing film may contain different structures, and may contain a ligand satisfying the configuration of (b) above and other general ligands respectively.

[0061] It is preferable that the ligand is derived from a compound represented by the following formula (1).

Chemical formula

[0062] Since the compound containing a halogen atom used for the ligand contains a crosslinkable group, the heat resistance of the ligand containing a halogen atom is improved. Therefore, when this is used in a composition for forming a metal-containing film, it is possible to form a metal-containing film containing a large amount of halogen atoms.

[0063] It is preferable that the compound represented by the general formula (1) contains at least one or more of an aromatic ring, a heteroaromatic ring, and an alicyclic structure.

[0064] Since the compound containing a halogen atom used for the ligand contains the above structure, the heat resistance of the ligand containing a halogen atom is further improved. Therefore, when this is used in a composition for forming a metal-containing film, it is possible to form a metal-containing film containing a large amount of halogen atoms.

[0065] R in the general formula (1) a is preferably a structure represented by the following formula (1-A). [Chemical formula] (In the above formula, X1 is a halogen atom or a monovalent organic group having 1 to 10 carbon atoms containing a halogen 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 x is a monovalent organic group having 2 to 20 carbon atoms containing a crosslinkable group selected from a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyloxy group, an epoxy group, an oxetanyl group, and a nitrile group, 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, and a hydroxyl group, n1 is 1 to 5, n2 is 1 to 4, n3 is 0 to 2, and * is the bonding part with X m1 .)

[0066] In the above formula (1-A), X1 is a halogen atom or a monovalent organic group having 1 to 10 carbon atoms containing a halogen atom, and a halogen atom or a halogenated hydrocarbon group having 1 to 10 carbon atoms is preferred. Specific examples of the halogenated hydrocarbon group include, for example, halogenated alkyl groups such as a trifluoromethyl group, a fluoromethyl group, a chloromethyl group, a bromoethyl group, and an iodoethyl group. When the above X1 contains a plurality of halogen atoms, the plurality of halogen atoms may be the same or different.

[0067] In the above formula (1-A), R X is a monovalent organic group having 2 to 20 carbon atoms containing a crosslinkable group selected from a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyloxy group, an epoxy group, an oxetanyl group, and a nitrile group, and specifically preferably contains the following structure.

[0068] [Chemical formula] (In the above general formulas (a-1) to (a-4), Ra 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.) [Chemical formula] (In the above general formula, R b is a hydrogen atom or a methyl group, and in the same formula, they may be the same as or different from each other. 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 arylalkyl group having 7 to 31 carbon atoms, and * represents a bonding site.) [Chemical formula] (In the formula, R e is a hydrogen atom or an organic group having 1 to 10 carbon atoms, and * indicates a bonding site.)

[0069] In the above formula (1-A), W is preferably an organic group having 5 to 20 carbon atoms containing any one of an aromatic ring, a heteroaromatic ring, and an alicyclic structure, and more preferably has the following structure. [Chemical formula] (In the above formula, R is any one of the above R x , R A , and X1, and * is a bonding site.)

[0070] From the viewpoint of heat resistance, in the above formula (1-A), it is more preferable that W contains an aromatic ring, and from the viewpoint of productivity, it is particularly preferable that it is a benzene ring or a naphthalene ring.

[0071] X in the general formula (1) m1 preferably contains one or more carbonyl groups.

[0072] When the compound containing a halogen atom used as a ligand includes the above structure, the heat resistance of the ligand containing a halogen atom is further improved. Therefore, when this is used in a composition for forming a metal-containing film, it becomes possible to form a metal-containing film containing a large amount of halogen atoms.

[0073] The above X m1 is more preferably a saturated hydrocarbon having 1 to 20 carbon atoms or an unsaturated hydrocarbon having 2 to 20 carbon atoms or a structure represented by the following formula (4).

Chemical formula

[0074] With such a structure, the heat resistance of the compound for forming a metal-containing film can be further improved.

[0075] In the above formula (1), m1 is 0 or 1. When m1 is 1, it becomes easier to form a resist underlayer film or an intermediate film that can contribute to improving the sensitivity while maintaining the LWR of the upper layer resist in EUV lithography. When m1 is 0, it becomes easier to form a resist underlayer film or an intermediate film that can transfer the resist pattern formed by EUV lithography to the substrate to be processed with high precision.

[0076] The compound represented by the general formula (1) contains one or more halogen atoms, preferably contains a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably contains a fluorine atom, a bromine atom, or an iodine atom, still more preferably contains a fluorine atom or an iodine atom, and particularly preferably contains an iodine atom.

[0077] Such a compound for forming a metal-containing film contains halogen atoms with high light absorption, so that the sensitizing effect by secondary electrons generated during exposure in EUV lithography can be more expected.

[0078] In particular, iodine atoms are preferable because they have a large atomic weight and thus have a high effect of suppressing acid diffusion from the upper-layer resist into the lower-layer resist film or the intermediate film, and have the characteristic that high sensitivity can be achieved while maintaining the LWR performance originally possessed by the upper-layer resist film.

[0079] Further, it is preferable that the compound for forming a metal-containing film of the present invention contains at least one selected from a metal compound represented by the following formula (3), and a hydrolyzate, condensate, and hydrolyzate condensate of the metal compound represented by the following formula (3) (hereinafter referred to as (a') metal-containing compound), and is a reaction product of the compound represented by the above formula (1). [Chemical formula] (In the formula, M is any one of Ti, Zr, and Hf. L is either a monodentate ligand or a polydentate ligand having 1 to 30 carbon atoms, X is a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, -NR a R b selected from a hydrolyzable group. 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.)

[0080] Such a compound for forming a metal-containing film can form a metal-containing film excellent in dry etching resistance to fluorine gas and oxygen gas when used in a composition for forming a metal-containing film.

[0081] [(a') metal-containing compound] (Hydrolyzable group) Examples of the hydrolyzable group X in the above formula (3) include a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, and -NR a Rb include R a and R b are each independently preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

[0082] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.

[0083] Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a t-butoxy group, etc.

[0084] Examples of the carboxylate group include an acetate group, a propionate group, a butyrate group, an n-hexanecarboxylate group, an n-octanecarboxylate group, etc.

[0085] Examples of the acyloxy group include an acetoxy group, an ethyroyloxy group, a propionyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amyryloxy group, an n-hexanecarbonyloxy group, an n-octanecarbonyloxy group, etc.

[0086] The above -NR a R b Examples thereof include an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dipropylamino group, etc.

[0087] The hydrolyzable group X is preferably an alkoxy group, more preferably an i-propoxy group, an n-butoxy group, or a t-butoxy group.

[0088] (monodentate ligand) Examples of the monodentate ligand L include a hydroxo ligand, a carboxy ligand, an amide ligand, an amine ligand, an ammonia ligand, an olefin ligand, etc.

[0089] Examples of the amide ligand include unsubstituted amide ligand (NH2), methylamide ligand (NHMe), dimethylamide ligand (NMe2), diethylamide ligand (NEt2), dipropylamide ligand (NPr2), and the like.

[0090] Examples of the amine ligand include pyridine, trimethylamine ligand, piperidine ligand, and the like.

[0091] Examples of the olefin ligand include chain olefins such as ethylene and propylene, and cyclic olefins such as cyclopentene, cyclohexene, and norbornene.

[0092] (Multidentate ligand) Examples of the multidentate ligand L include ligands derived from hydroxy acid esters, ligands derived from β-diketones, ligands derived from β-ketoesters, ligands derived from α,α-dicarboxylic acid esters, hydrocarbons having a π bond, diphosphines, and the like.

[0093] Examples of the hydroxy acid ester include glycolic acid ester, lactic acid ester, 2-hydroxycyclohexane-1-carboxylic acid ester, salicylic acid ester, and the like.

[0094] Examples of the β-diketone include acetoacetic acid ester, α-alkyl-substituted acetoacetic acid ester, β-ketopentanoic acid ester, benzoylacetic acid ester, 1,3-acetonedicarboxylic acid ester, and the like.

[0095] Examples of the α,α-dicarboxylic acid ester include malonic acid diester, α-alkyl-substituted malonic acid diester, α-cycloalkyl-substituted malonic acid diester, α-aryl-substituted malonic acid diester, and the like.

[0096] Examples of the hydrocarbon having the above π bond include chain dienes such as butadiene and isoprene, cyclic dienes such as cyclopentadiene, methylcyclopentadiene, pentamethylcyclopentadiene, cyclohexadiene, and norbornadiene, and aromatic hydrocarbons such as benzene, toluene, xylene, hexamethylbenzene, naphthalene, and indene.

[0097] Examples of the diphosphine include 1,1-bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, 1,1'-bis(diphenylphosphino)ferrocene, and the like.

[0098] In the above general formula (3), a + b = 2 to 4, and a and b are integers from 0 to 4. As a, 0 to 4 is preferable, and 2 or 4 is more preferable. As b, 0 to 4 is preferable, and 0 or 2 or 4 is more preferable. By setting a and b within the above range, the stability of the compound for forming a metal-containing film of the present invention can be enhanced.

[0099] Preferable examples of the metal compound represented by the formula (3) include the following.

[0100] Examples of the titanium-containing compound include diisopropoxybis(2,4-pentanedionato)titanium(IV), tetra-n-butoxytitanium(IV), tetra-n-propoxytitanium(IV), tetraisopropoxytitanium(IV), tri-n-butoxymonostearatetitanium(IV), titanium(IV) butoxide 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), and the like.

[0101] Examples of the zirconium-containing compound include dibutoxybis(ethylacetoacetate)zirconium(IV), din-butoxybis(2,4-pentanedionato)zirconium(IV), tetra-n-butoxyzirconium(IV), tetra-n-propoxyzirconium(IV), tetraisopropoxyzirconium(IV), aminopropyltriethoxyzirconium(IV), 2-(3,4-epoxycyclohexyl)ethyltrimethoxyzirconium(IV), γ-glycidoxypropyltrimethoxyzirconium(IV), 3-isocyanopropyltrimethoxyzirconium(IV), triethoxymono(2,4-pentanedionato)zirconium(IV), tri-n-propoxymono(2,4-pentanedionato)zirconium(IV), triisopropoxymono(2,4-pentanedionato)zirconium(IV), tri(3-methacryloxypropyl)methoxyzirconium(IV), tri(3-acryloxypropyl)methoxyzirconium(IV), and the like.

[0102] Examples of the hafnium-containing compound include diisopropoxybis(2,4-pentanedionato)hafnium(IV), tetrabutoxyhafnium(IV), tetraisopropoxyhafnium(IV), tetraethoxyhafnium(IV), dichlorobis(cyclopentadienyl)hafnium(IV), and the like.

[0103] Among them, metal alkoxides, metal carboxylates, and metal acetates are more preferable.

[0104] In the synthesis reaction of the compound for forming a metal-containing film, in addition to the metal compound, a compound that can be a monodentate ligand or a multidentate ligand in the compound for forming a metal-containing film (hereinafter referred to as (b') ligand-forming compound) may be added.

[0105] Examples of the compound for forming the ligand (b’) include organic compounds derived from hydroxy ligands, carboxy ligands, amide ligands, amine ligands, ammonia ligands, olefin ligands, etc., as exemplified for L in the general formula (3) above, ligands derived from hydroxy acid esters, ligands derived from β-diketones, ligands derived from β-ketoesters, ligands derived from α,α-dicarboxylic acid esters, etc., and compounds having a compound with a plurality of hydroxy groups, etc.

[0106] In the compound for forming a metal-containing film of the present invention, the content of the ligand derived from the structure represented by the above formula (1) is preferably 10 mol% to 90 mol%, more preferably 20 mol% to 80 mol%, and still more preferably 25 mol% to 75 mol% of the total ligands coordinated to the metal atom. Ligands other than the compound represented by the above formula (1), for example, the ligand-forming compound (b’) and ligands derived from alkoxy groups having 1 to 10 carbon atoms preferably have a content of 0 mol% to 90 mol%, and more preferably 20 mol% to 80 mol% of the total ligands coordinated to the metal atom.

[0107] Furthermore, in the synthesis reaction of the compound for forming a metal-containing film of the present invention, a silicon-containing compound (c) may be added in addition to the ligand-forming compound (b’).

[0108] By substituting the hydrolyzable group of the metal-containing compound (a’) with the silicon-containing compound (c), the stability of the compound for forming a metal-containing film of the present invention in the metal-containing film-forming composition can be improved.

[0109] Examples of the silicon-containing compound (c) include the structure of the following formula (2), etc.

Chemical formula

[0110] As the silicon-containing compound, any one of the following compounds is more preferable, and trimethylsilanol is more preferable from the viewpoint of productivity. [Chemical formula] (In the above formula, * represents a bonding portion with a metal atom.)

[0111] When the compound for forming a metal-containing film of the present invention contains a ligand derived from the structure represented by the above formula (1) and a ligand derived from (c) a silicon-containing compound, in the compound for forming a metal-containing film of the present invention, the content of the ligand derived from the structure represented by the above formula (1) is preferably 10 mol% to 100 mol% of the total ligands coordinated to the metal atom, more preferably 20 mol% to 80 mol%, and even more preferably 25 mol% to 75 mol%. The ligand derived from (c) a silicon-containing compound preferably has a content of 10 mol% to 90 mol% of the total ligands coordinated to the metal atom, more preferably 20 mol% to 80 mol%, and even more preferably 25 mol% to 75 mol%. Ligands other than (b') the ligand-forming compound and (c) the silicon-containing compound, for example, ligands derived from alkoxy groups having 1 to 10 carbon atoms, preferably have a content of 0 mol% to 90 mol% of the total ligands coordinated to the metal atom, and a content of 0 mol% to 75 mol% is more preferable.

[0112] The method for synthesizing the compound for forming a metal-containing film of the present invention is not particularly limited. For example, (a') a metal alkoxide, a metal carboxylate, or a metal acetylacetonate (acac) can be used as the metal-containing compound, and an alkoxy, carboxy, or acac metal is obtained by reacting with a ligand derived from the compound represented by the above formula (1). (a') After hydrolytic condensation of the metal-containing compound, it may be reacted with a ligand derived from the compound represented by the above formula (1), or (a') after reacting the metal-containing compound with a ligand derived from the compound represented by the above formula (1), hydrolytic condensation may be carried out. When it is difficult to control hydrolytic condensation, it may be reacted with a ligand derived from the compound represented by the above formula (1) in a non-aqueous environment. These are preferably adjusted as appropriate according to the properties required for the compound for forming a metal-containing film and the metal-containing film of the present invention. (c) When a silicon-containing compound and the compound represented by the above formula (1) are used as a ligand, it is preferable to react (a') the metal-containing compound with (c) the silicon-containing compound and then react with a ligand derived from the compound represented by the above formula (1).

[0113] Examples of the method for performing a hydrolytic condensation reaction using (a') a metal-containing compound include a method of subjecting (a') the metal-containing compound to a hydrolytic condensation reaction in a solvent containing water. In this case, another compound having a hydrolyzable group may be added as necessary. Further, as a catalyst for the hydrolytic condensation reaction, an acid such as acetic acid may be added. The lower limit of the amount of water used in this hydrolytic condensation reaction is preferably 0.2 times the mole, more preferably 1 time the mole, and even more preferably 3 times the mole, relative to the hydrolyzable group possessed by (a') the metal-containing compound and the like. The upper limit of the amount of water is preferably 20 times the mole, more preferably 15 times the mole, and even more preferably 10 times the mole.

[0114] The solvent used in the synthesis reaction of the compound for forming a metal-containing film of the present invention is not particularly limited, and for example, the same solvents as those exemplified as the following (B) organic solvents can be used. Typical solvents and solvent mixtures include those containing an ester, ether or alcohol functional group, for example, a mixture of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) in a volume ratio of 70 / 30. Examples of other solvents that can be used include butanediol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, 1-butanol, 2-butanol, 2-methyl-1-propanol, 4-methyl-2-pentanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diamyl ether, isoamyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and the like.

[0115] <Composition for forming a metal-containing film> The present invention also provides a composition for forming a metal-containing film that functions as a resist underlayer film material or a resist intermediate film material used in semiconductor manufacturing, which contains (A) the above-described compound for forming a metal-containing film and (B) an organic solvent.

[0116] <(A) Compound for forming a metal-containing film> (A) As the compound for forming a metal-containing film, the compound for forming a metal-containing film of the present invention described above may be used. In the composition, the blending amount of component (A) is not particularly limited. For example, it can be 1 to 20 parts by mass, preferably 2 to 10 parts by mass, based on 100 parts by mass in total of component (A) and component (B).

[0117] <(B) Organic solvent> As the (B) organic solvent that can be used in the composition for forming a metal-containing film of the present invention, there is no particular limitation as long as it can dissolve or disperse the above-mentioned (A) compound for forming a metal-containing film, and in the case of containing, the (C) cross-linking agent, (D) acid generator, (E) surfactant, (B') high-boiling solvent, and other additives described below.

[0118] Specifically, for example, the organic solvents described in paragraphs

[0091] to

[0092] of JP-A-2007-199653 can be added. More specifically, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, 2-heptanone, cyclopentanone, cyclohexanone, and γ-butyrolactone, or a mixture containing one or more of these is preferably used.

[0119] The blending amount of the organic solvent is preferably 200 to 10,000 parts, more preferably in the range of 250 to 5,000 parts, based on 100 parts by mass of the (A) compound for forming a metal-containing film.

[0120] <(B') High-boiling solvent> In the composition for forming a metal-containing film of the present invention, the (B) organic solvent may contain a (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.

[0121] For example, as the (B) organic solvent, a mixture of one or more organic solvents having a boiling point of less than 180 °C and one or more organic solvents having a boiling point of 180 °C or higher ((B') high-boiling solvent) may be used.

[0122] (B’) As the high-boiling solvent, there are no particular restrictions as long as it can dissolve each component of the composition for forming a metal-containing film of the present invention, and examples include hydrocarbons, alcohols, ketones, esters, ethers, chlorinated solvents, etc. Specific examples include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3 - hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, n - nonyl acetate, monohexyl ether, ethylene glycol mono - 2 - ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono - n - butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol - n - butyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono - n - propyl ether, dipropylene glycol mono - n - butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono - n - propyl ether, tripropylene glycol mono - n - butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol methyl - n - propyl ether, dipropylene glycol methyl ether acetate, 1,4 - butanediol diacetate, 1,3 - butylene glycol diacetate, 1,Examples thereof include 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., and these may be used alone or in combination.

[0123] (B’) The high-boiling solvent may be appropriately selected from, for example, the above-mentioned ones according to the temperature at which the composition for forming a metal-containing film of the present invention is heat-treated. The boiling point of the high-boiling solvent is preferably 180°C to 300°C, and more preferably 200°C to 300°C. At such a boiling point, there is no risk that the volatilization during baking (heat treatment) will become too fast, so it is possible to suppress the occurrence of defects caused by drying during film formation. Also, at such a boiling point, it will not remain in the film without volatilizing even after baking, so there is no risk of adversely affecting the film physical properties such as etching resistance.

[0124] Also, when using the (B’) high-boiling solvent, the blending amount is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the organic solvent having a boiling point of less than 180°C. With such a blending amount, sufficient thermal fluidity can be imparted during baking, and it does not remain in the film and does not lead to deterioration of film physical properties such as etching resistance, so it is preferable.

[0125] <Other components> The composition for forming a metal-containing film is a composition for forming a metal-containing film that can be used as a resist underlayer film or intermediate film used in a multilayer resist method, and it may contain one or more of the above (A) compounds for forming a metal-containing film, (B) organic solvents, and if necessary, at least one or more of (C) crosslinking agent, (D) acid generator, (E) surfactant, (B’) high-boiling solvent.

[0126] Hereinafter, components that can be included in the composition for forming a metal-containing film of the present invention, other than the above (A) compounds for forming a metal-containing film and (B) organic solvents, will be described.

[0127] [(C) Crosslinking agent] In addition, in the composition for forming a metal-containing film of the present invention, a (C) crosslinking agent can be added in order to enhance curability and further suppress intermixing with the resist upper layer film.

[0128] The crosslinking agent is not particularly limited, and various known types of crosslinking agents can be widely used. As an 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 exemplified.

[0129] 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, based on 100 parts of the above (A) compound for forming a metal-containing film. If the addition amount is 5 parts or more, sufficient curability can be exhibited and intermixing with the resist upper layer film can be suppressed. On the other hand, if the addition amount is 50 parts or less, there is no risk of deterioration of dry etching resistance due to a low ratio of the (A) compound for forming a metal-containing film in the composition.

[0130] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylated melamine, hexabutoxymethylated melamine, their alkoxy and / or hydroxy-substituted products, and their partial self-condensates.

[0131] Specific examples of the glycoluril-based crosslinking agent include tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, their alkoxy and / or hydroxy-substituted products, and their partial self-condensates.

[0132] As the benzoguanamine-based crosslinking agent, specifically, tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, their alkoxy and / or hydroxy-substituted products, and their partial self-condensates can be exemplified.

[0133] As the urea-based crosslinking agent, specifically, dimethoxymethylated dimethoxyethyleneurea, its alkoxy and / or hydroxy-substituted products, and their partial self-condensates can be exemplified.

[0134] As the β-hydroxyalkylamide-based crosslinking agent, specifically, N,N,N’,N’-tetra(2-hydroxyethyl) adipic acid amide can be exemplified.

[0135] As the isocyanurate-based crosslinking agent, specifically, triglycidyl isocyanurate, triallyl isocyanurate can be exemplified.

[0136] As the aziridine-based crosslinking agent, specifically, 4,4’-bis(ethyleneiminocarbonylamino) diphenylmethane, 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl) propionate] can be exemplified.

[0137] As the oxazoline-based crosslinking agent, specifically, 2,2’-isopropylidene bis(4-benzyl-2-oxazoline), 2,2’-isopropylidene bis(4-phenyl-2-oxazoline), 2,2’-isopropylidene bis(4-phenyl-2-oxazoline), 2,2’-methylene bis 4,5-diphenyl-2-oxazoline, 2,2’-methylene bis-4-phenyl-2-oxazoline, 2,2’-methylene bis-4-tert butyl-2-oxazoline, 2,2’-bis(2-oxazoline), 1,3-phenylene bis(2-oxazoline), 1,4-phenylene bis(2-oxazoline), 2-isopropenyl oxazoline copolymer can be exemplified.

[0138] Specific examples of the epoxy crosslinking agent include diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, poly(glycidyl methacrylate), trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether.

[0139] Specific examples of the phenolic crosslinking agent include compounds represented by the following general formula (10).

Chemical formula

[0140] 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, and more preferably 2 or 3. Specific examples of Q include methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, and eicosane. R 1 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, octyl group, ethylhexyl group, decyl group, and eicosanyl group, and a hydrogen atom or a methyl group is preferred. 16

[0141] As examples of the compound represented by the above general formula (10), specifically, the following compounds can be exemplified. Among these, from the viewpoints of curability of the adhesion film and improvement of film thickness uniformity, hexamethoxymethylated products of triphenolmethane, triphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferable.

[0142]

Chemical formula

[0143]

Chemical formula

[0144] <(D) Acid generator> In the composition for forming a metal-containing film of the present invention, a (D) acid generator can be added in order to further accelerate the curing reaction of the above (A) compound for forming a metal-containing film. Acid generators include those that generate acid by thermal decomposition and those that generate acid by light irradiation, and any of them can be added. Specifically, the materials described in paragraphs

[0061] to

[0085] of JP-A-2007-199653 can be added, but are not limited thereto.

[0145] The above acid generator can be used alone or in combination of two or more. When adding the acid generator, the addition amount is preferably 0.05 to 50 parts, more preferably 0.1 to 10 parts, based on 100 parts by mass of the above (A) compound for forming a metal-containing film.

[0146] <(E) Surfactant> In the composition for forming a metal-containing film of the present invention, an (E) surfactant can be added in order to improve the coatability in spin coating. Examples of the surfactant include those described in paragraphs

[0142] to

[0147] Those described can be used. When adding a surfactant, the addition amount is preferably 0.01 to 10 parts, more preferably 0.05 to 5 parts, per 100 parts by mass of the above-mentioned (A) compound for forming a metal-containing film.

[0147] <Method for forming a metal-containing film> In the present invention, there is provided a method for forming a filling film that functions as a resist underlayer film, an intermediate film, or a planarization film for semiconductor manufacturing of a multilayer resist film used in lithography, using the above-described composition for forming a metal-containing film.

[0148] In the method for forming a metal-containing film using the composition for forming a metal-containing film of the present invention, the above-described composition for forming a metal-containing film 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 embedding characteristics can be obtained. After spin coating, the solvent is evaporated, and baking (heat treatment) is performed to promote a crosslinking reaction in order to prevent mixing with the resist upper layer film and the resist intermediate film. 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 in the wafer process of lithography is preferably 600°C or lower, more preferably 500°C or lower.

[0149] Further, in the method for forming a metal-containing film using the composition for forming a metal-containing film of the present invention, the composition for forming a metal-containing film of the present invention is coated on a substrate to be processed by the spin coating method or the like as described above, and the metal-containing film can also be formed by baking and curing the composition for forming a metal-containing film in an atmosphere having an oxygen concentration of 0.1% by volume or more and 21% by volume or less.

[0150] By firing the composition for forming a metal-containing film of the present invention in such an oxygen atmosphere, a sufficiently cured film can be obtained. The atmosphere during baking may be air, but it is preferable to enclose an inert gas such as N2, Ar, or He to reduce oxygen in order to prevent oxidation of the metal-containing film. In order to prevent oxidation, it is necessary to control the oxygen concentration, preferably 1000 ppm or less, more preferably 100 ppm or less (by volume). Preventing oxidation of the metal-containing film during baking is preferable because it does not increase absorption or reduce etching resistance.

[0151] <Pattern formation method using a composition for forming a metal-containing film> Next, a pattern formation method using the composition for forming a metal-containing film of the present invention will be described.

[0152] <Two-layer resist process> In the present invention, as a pattern formation method by a two-layer resist process using the above composition for forming a metal-containing film, (I-1) A step of forming a metal-containing film by applying the above composition for forming a metal-containing film on a substrate to be processed and then performing heat treatment, (I-2) A step of forming a resist upper layer film on the metal-containing film using a photoresist material, (I-3) After pattern exposure of the resist upper layer film, developing with a developer to form a pattern in the resist upper layer film, (I-4) A step of transferring the pattern to the metal-containing film by dry etching using the resist upper layer film having the pattern as a mask, and (I-5) A step of processing the substrate to be processed using the metal-containing film having the pattern as a mask to form a pattern on the substrate to be processed A pattern formation method having the above steps is provided.

[0153] In the above two-layer resist process, since the upper resist film exhibits etching resistance to chlorine-based gases, in the above two-layer resist process, it is preferable to perform dry etching of the metal-containing film using the upper resist film as a mask with an etching gas mainly composed of chlorine-based gases.

[0154] In order to ensure adhesion to the upper resist film, an adhesion film may be formed between the upper resist film and the metal-containing film of the present invention. As the adhesion film, an organic film or a silicon-containing film containing polysiloxane can be used.

[0155] The pattern formation method by the resist process using the composition for forming the metal-containing film of the present invention is useful for improving the exposure sensitivity of the upper resist film. Therefore, it is preferably used as a lower layer film close to the upper resist film, and more preferably used directly under the upper resist film. When an adhesion film is used between the upper resist film and the metal-containing film, the thickness of the adhesion film is preferably 20 nm or less, more preferably 15 nm or less, and even more preferably 10 nm or less. The thinner the thickness of the adhesion film, the greater the contribution of the metal-containing film to improving the exposure sensitivity of the upper resist film, which is preferable.

[0156] <Three-layer resist process> Further, in the present invention, as a pattern formation method by a three-layer resist process using such a composition for forming a metal-containing film, (II-1) A step of forming an organic resist lower layer film on a substrate to be processed, (II-2) A step of forming a metal-containing film by applying the above composition for forming a metal-containing film on the organic resist lower layer film and then performing heat treatment, (II-3) A step of forming an upper resist film using a photoresist material on the metal-containing film, (II-4) A step of pattern-exposing the upper resist film and then developing it with a developer to form a pattern in the upper resist film, (II-5) A step of transferring the pattern to the metal-containing film by dry etching using the upper resist film on which the pattern is formed as a mask, (II-6) A step of transferring a pattern to the organic resist underlayer film by dry etching using the metal-containing film onto which the pattern has been transferred as a mask, and (II-7) A step of processing the substrate to be processed using the organic resist underlayer film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed provided is a pattern formation method characterized by comprising the steps.

[0157] The pattern formation method by the three-layer resist process of the present invention will be described with reference to FIG. 1. First, after forming an organic resist underlayer film 2 on a substrate 1 to be processed (I-A), a metal-containing film 3 (I-B) is formed as a resist intermediate film using the composition for forming a metal-containing film of the present invention, and a resist upper layer film 4 is formed thereon using a photoresist material (I-C). Next, exposure P is performed on the resist upper layer film 4 using a mask 5 (I-D), and PEB (post-exposure bake) is performed (I-E). Next, development is performed to form a resist upper layer film pattern 4a (I-F). Next, using the resist upper layer film pattern 4a as a mask, the metal-containing film 3 is dry-etched to form a metal-containing film pattern 3a (I-G). Next, after removing the resist upper layer film pattern 4a, using the metal-containing film pattern 3a as a mask, the organic resist underlayer film 2 is dry-etched to form an organic resist underlayer film pattern 2a (I-H). Further, after removing the metal-containing film pattern 3a, using the organic resist underlayer film pattern 2a as a mask, the substrate 1 to be processed is etched to form a pattern 1a (I-I).

[0158] Since the metal-containing film of the three-layer resist process exhibits etching resistance to an oxygen-based gas, in the three-layer resist process, it is preferable to perform dry etching of the organic resist underlayer film using the metal-containing film as a mask using an etching gas mainly composed of an oxygen-based gas.

[0159] Examples of the organic resist underlayer film material that can be used for the above-described organic resist underlayer film include those known as the underlayer film for the three-layer resist method or the two-layer resist method using a silicon resist composition. In addition to the 4,4'-(9-fluorenylidene)bisphenol novolak resin (molecular weight: 11,000) described in JP-A-2005-128509, a number of resins such as novolak resins, which are known as the resist underlayer film materials for the two-layer resist method and the three-layer resist method, can be used. When it is desired to increase the heat resistance compared to ordinary novolak, a polycyclic skeleton such as 6,6'-(9-fluorenylidene)-di(2-naphthol) novolak resin can be incorporated, or a polyimide-based resin can also be selected (for example, see JP-A-2004-153125).

[0160] The above-described organic resist underlayer film can be formed on a 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 resist underlayer film by a spin coating method or the like, it is desirable to bake it 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.

[0161] Instead of the above-described organic resist underlayer film material, an organic hard mask formed by a CVD method or an ALD method can also be applied.

[0162] In addition, in the present invention, a pattern forming method by a three-layer resist process using such a composition for forming a metal-containing film is provided. A metal-containing film is formed on a substrate to be processed using the composition for forming a metal-containing film, 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 metal-containing film, a resist upper layer film is formed on the inorganic hard mask using a photoresist material, the resist upper layer film is pattern-exposed and then developed with a developer to form a pattern in the resist upper layer film, the inorganic hard mask intermediate film is pattern-transferred by dry etching using the resist upper layer film with the pattern as a mask, the metal-containing film is pattern-transferred by dry etching using the inorganic hard mask intermediate film with the pattern as a mask, and the substrate to be processed is processed using the metal-containing film with the pattern as a mask to form a pattern on the substrate to be processed.

[0163] <Four-layer resist process> In addition, in the present invention, as a pattern forming method by a four-layer resist process using such a composition for forming a metal-containing film, (III-1) A step of forming a metal-containing film by applying the above composition for forming a metal-containing film on a substrate to be processed and then performing heat treatment; (III-2) A step of forming an inorganic hard mask intermediate film selected from a silicon-containing resist intermediate film, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film; (III-3) A step of forming an organic thin film (for example, an organic antireflection film (BARC) or an adhesion film) on the inorganic hard mask intermediate film; (III-4) A step of forming a resist upper layer film on the organic thin film using a photoresist material; (III-5) A step of pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern in the resist upper layer film; (III-6) A step of pattern-transferring the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film with the pattern as a mask; (III-7) Using the inorganic hard mask intermediate film onto which the pattern has been transferred as a mask, transferring the pattern to the metal-containing film by dry etching, and (III-8) Using the metal-containing film onto which the pattern has been formed as a mask to process the substrate to be processed and forming a pattern on the substrate to be processed A pattern formation method characterized by having the above.

[0164] At this time, it is preferable that the inorganic hard mask intermediate film is formed by a CVD method or an ALD method.

[0165] When the above inorganic hard mask is formed by a CVD method or an ALD method, a fine pattern can be formed on the workpiece with higher accuracy.

[0166] When a silicon-containing resist intermediate film is used for the inorganic hard mask intermediate film in the above pattern formation method, as the silicon-containing resist intermediate film, a polysiloxane-based intermediate film is also preferably used. By giving the silicon-containing resist intermediate film an antireflection effect, reflection can be suppressed. Especially for 193 nm exposure, when a material containing many aromatic groups as an organic film and having a high etching selectivity with the substrate is used, the k value becomes high and the substrate reflection becomes high. However, by giving an absorption such that an appropriate k value is obtained as the silicon-containing resist intermediate film, it becomes possible to suppress reflection and reduce the substrate reflection to 0.5% or less. As the silicon-containing resist intermediate film having an antireflection effect, for 248 nm and 157 nm exposure, anthracene, and for 193 nm exposure, a polysiloxane having a phenyl group or an absorbing group having a silicon-silicon bond pendant and crosslinked by an acid or heat is preferably used.

[0167] As an inorganic hard mask intermediate film, an inorganic hard mask may be formed. In this case, at least, a metal-containing film is formed on a workpiece using the composition for forming a metal-containing film of the present invention, 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, a resist upper layer film is formed on the inorganic hard mask using a photoresist composition, a circuit pattern is formed on the resist upper layer film, the inorganic hard mask is etched using the resist upper layer film on which the pattern is formed as a mask, the metal-containing film is etched using the inorganic hard mask on which the pattern is formed as a mask, and further, the workpiece is etched using the metal-containing film on which the pattern is formed as a mask to form a pattern on the workpiece, whereby a semiconductor device circuit pattern can be formed on a substrate.

[0168] As described above, when forming an inorganic hard mask on a 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, as a method for forming a silicon nitride film, it is described in JP-A-2002-334869 and WO 2004 / 066377. The film thickness of the inorganic hard mask is preferably 5 to 200 nm, more preferably 10 to 100 nm. Further, as the inorganic hard mask, an SiON film having a high effect as an antireflection film is most preferably used. Since the substrate temperature when forming the SiON film is 300 to 500°C, the metal-containing film needs to withstand a temperature of 300 to 500°C. The composition for forming a metal-containing film used in the present invention has high heat resistance and can withstand a high temperature of 300°C to 500°C, so 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 is possible.

[0169] As described above, a photoresist film may be formed as a resist upper layer film on the inorganic hard mask, but an organic anti-reflection film (BARC) or an adhesion film may be spin-coated on the inorganic hard mask, and a photoresist film may be formed thereon. In particular, when a SiON film is used as the inorganic hard mask, it is possible to suppress reflection even in immersion lithography with a high NA exceeding 1.0 by the two-layer anti-reflection film of the SiON film and BARC. Another merit of forming BARC is that it has the effect of reducing the pull-off of the photoresist pattern directly above the SiON film.

[0170] In the above pattern formation method, the resist upper layer film may be either positive or negative, and the same photoresist composition commonly used can be used. Further, the photoresist composition may contain metal atoms such as Sn, In, Ga, Ge, Al, Ce, La, Cs, Zr, Hf, Ti, Bi, Sb, and Zn. When forming the resist upper layer film with the above photoresist composition, it may be formed by spin coating or by vapor deposition treatment by CVD or ALD.

[0171] When forming the photoresist composition by spin coating, pre-baking is performed after resist coating, and the range of 60 to 180 °C for 10 to 300 seconds is preferred. Thereafter, exposure is performed according to a conventional method, post-exposure baking (PEB), development is performed, and a resist pattern is obtained. The thickness of the resist upper layer film is not particularly limited, but 10 to 500 nm, particularly 20 to 400 nm is preferred.

[0172] When forming a photoresist composition by vapor deposition treatment using CVD or ALD, the resist composition is a 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 metal oxide-containing film may be a photosensitive organometallic oxide film such as an organic tin oxide (e.g., haloalkyl Sn, alkoxyalkyl Sn, or amidoalkyl Sn). Some specific examples of suitable precursors include trimethyltin chloride, dimethyltin dichloride, methyltin trichloride, tris(dimethylamino)methyltin(IV), and (dimethylamino)trimethyltin(IV).

[0173] The metal oxide film may be deposited by PECVD or PEALD, for example, using a Lam Vector (registered trademark) tool. In the ALD example, the Sn oxide precursor is separated from the O precursor / plasma. The deposition temperature is preferably in the range of 50°C to 600°C. The deposition pressure is preferably between 100 and 6000 mTorr. The flow rate of the precursor liquid of the metal oxide-containing film (e.g., the organic tin oxide precursor) may be 0.01 to 10 cmm, and the gas flow rate (CO2, CO, Ar, N2) may be 100 to 10000 sccm. The plasma power may be 200 to 1000 W per 300 mm wafer station using high-frequency plasma (e.g., 13.56 MHz, 27.1 MHz, or a higher frequency). The deposition thickness is preferably 100 to 2000 Å.

[0174] Examples of the exposure light include high-energy rays with a wavelength of 300 nm or less, specifically, excimer lasers of 248 nm, 193 nm, 157 nm, soft X-rays of 3 to 20 nm, electron beams, X-rays, etc.

[0175] As a method for forming a pattern on the resist upper layer film, a pattern can be formed by photolithography with a wavelength of 5 nm or more and 300 nm or less, direct drawing by an electron beam, nanoimprinting, or a combination thereof. In the present invention, EUV light is most preferred.

[0176] In addition, it is preferable that the development method in the pattern formation method be development with an alkali or an organic solvent.

[0177] Next, etching is performed using the obtained resist pattern as a mask. For etching the silicon-containing resist intermediate layer and the inorganic hard mask in the three-layer resist process, a fluorocarbon-based gas is used with the upper-layer resist pattern as a mask. Thereby, a silicon-containing resist intermediate layer pattern and an inorganic hard mask pattern are formed.

[0178] Next, etching of the metal-containing film is performed using the obtained silicon-containing resist intermediate layer pattern or inorganic hard mask pattern as a mask. It is preferable to perform the etching of the metal-containing film using an etching gas mainly composed of a chlorine-based gas.

[0179] Etching of the next workpiece can also be performed by a conventional method. For example, if the workpiece is SiO2, SiN, or a silica-based low dielectric constant insulating film, etching mainly using a fluorocarbon-based gas is performed. When the substrate processing is etched with a fluorocarbon-based gas, the silicon-containing resist intermediate layer pattern in the three-layer resist process is peeled off simultaneously with the substrate processing.

[0180] The metal-containing film obtained by the composition for forming a metal-containing film of the present invention is characterized by excellent etching resistance during etching of these workpieces.

[0181] Note that the workpiece (workpiece substrate) is not particularly limited, and substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc., and those with a processed layer formed on the substrate are used. As the processed layer, various Low-k films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, etc., and their stopper films are used, and they can usually be formed to a thickness of 50 to 10,000 nm, particularly 100 to 5,000 nm. When forming the processed layer, substrates and processed layers made of different materials are used.

[0182] <Multilayer resist process> Furthermore, in the present invention, as a pattern formation method by a multilayer resist process using such a composition for forming a metal-containing film, (IV-1) A step of forming a metal-containing film by applying the above composition for forming a metal-containing film on a substrate to be processed and then performing heat treatment, (IV-2) A step of forming an organic intermediate film on the metal-containing film, (IV-3) A step of forming 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 on the organic intermediate film, (IV-4) A step of forming a resist upper layer film using a photoresist material on the silicon-containing resist intermediate film or the organic thin film, (IV-5) A step of pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern in the resist upper layer film, (IV-6) A step of 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 using the resist upper layer film having the pattern as a mask, (IV-7) A step of transferring the pattern to the organic intermediate film by dry etching using the silicon-containing resist intermediate film or the inorganic hard mask intermediate film having the pattern as a mask, (IV-8) A step of transferring the pattern to the metal-containing film by dry etching using the organic intermediate film as a mask, and (IV-9) A step of processing the substrate to be processed using the metal-containing film having the pattern as a mask to form a pattern on the substrate to be processed A pattern formation method characterized by comprising the above steps is provided.

[0183] As an example of a pattern formation method by a multilayer resist process using such a composition for forming a metal-containing film, a metal-containing film is formed on a substrate to be processed using the above composition for forming a metal-containing film, an organic intermediate film is formed on the metal-containing film using an organic resist lower layer film material, a silicon-containing resist intermediate film is formed on the organic intermediate film using a silicon-containing resist intermediate film material, and if necessary, an organic antireflection film (BARC) or an adhesion film is formed on the silicon-containing resist intermediate film. A resist upper layer film is formed on the silicon-containing film or the BARC using a photoresist material. After pattern exposure of the resist upper layer film, development is performed with a developer to form a pattern in the resist upper layer film. Using the resist upper layer film in which the pattern is formed as a mask, the pattern is transferred to the BARC or the adhesion film and the silicon-containing resist intermediate film by dry etching. Using the silicon-containing resist intermediate film in which the pattern is transferred as a mask, the pattern is transferred to the organic intermediate film by dry etching. Using the organic intermediate film as a mask, the pattern is transferred to the metal-containing film. Using the metal-containing film in which the pattern is formed as a mask, the substrate to be processed is processed to form a pattern on the substrate to be processed. A pattern formation method characterized by having such steps can be mentioned.

[0184] Examples of the organic resist lower layer film material that can be used for the above organic intermediate film include those known as lower layer films for the three-layer resist method or the two-layer resist method using a silicon resist composition. In addition to the 4,4'-(9-fluorenylidene)bisphenol novolak resin (molecular weight 11,000) described in JP-A-2005-128509, a number of resins including novolak resins, which are known as resist lower layer film materials for the two-layer resist method and the three-layer resist method, can be used. Also, when it is desired to increase the heat resistance compared to ordinary novolak, a polycyclic skeleton such as 6,6'-(9-fluorenylidene)-di(2-naphthol) novolak resin can be incorporated, and a polyimide-based resin can also be selected (for example, JP-A-2004-153125).

[0185] The above-mentioned organic intermediate film can be formed on a 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 lower layer film by a spin coating method or the like, it is desirable 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.

[0186] Instead of the above-mentioned organic resist lower layer film material, an organic hard mask formed by a CVD method or an ALD method can also be applied.

[0187] Since the organic intermediate film of the above-mentioned multilayer resist process exhibits etching resistance to chlorine-based gases, in the above-mentioned multilayer resist process, it is preferable to perform dry etching of the metal-containing film using the organic intermediate film as a mask with an etching gas mainly composed of chlorine-based gases.

Example

[0188] Hereinafter, the present invention will be described more specifically by showing synthesis examples, examples, and comparative examples, but the present invention is not limited thereto.

[0189] [Synthesis of Compounds (A-1) to (A-18) for Forming Metal-Containing Films] In the following synthesis examples, the following organic group raw material groups G: (G1) to (G15) and silicon-containing organic group raw material groups H: (H1) to (H2) were used.

[0190] Raw material group G: (G1) to (G15) are shown below.

Chemical formula

[0191] Raw material group H: (H1) to (H2) are shown below.

Chemical formula

[0192] As the metal source M, the following metal compounds were used. (M1): Hafnium(IV) n-butoxide (M2): Titanium(IV) tetraisopropoxide (M3): Zirconium(IV) tetrabutoxide (80 wt% 1-butanol solution)

[0193] [Synthesis Example 1] Synthesis of Compound (A-1) for Forming Metal-Containing Film Under a nitrogen atmosphere, 23.5 g of hafnium(IV) n-butoxide (M1) was dissolved in 25.5 g of a PGMEA / PGME (weight ratio 70 / 30) solution, and while stirring, the reaction temperature was set to 60 °C and stirring was continued for 2 hours. Next, a mixture in which 21.6 g of Compound G1 was suspended in 22.0 g of a PGMEA / PGME (weight ratio 70 / 30) solution was added to the reaction system, and stirring was continued for 1 hour while maintaining the reaction temperature at 60 °C. After cooling to room temperature, the obtained reaction solution was filtered through a 0.45 μm PTFE filter to obtain a PGMEA / PGME solution of Compound (A-1) for forming a metal-containing film. The concentration of components other than the solvent in the solution was 24% by mass.

[0194] [Synthesis Examples 2 to 15] Synthesis of Compounds (A-2) to (A-12), Compounds (R-1) to (R-3) for Comparative Examples Compounds (A-2) to (A-12) and compounds (R-1) to (R-3) for comparative examples shown in Table 1 were obtained under the same reaction conditions as in Synthesis Example 1, except that the above metal source M and the above compound group G were used in the amounts shown in Table 1.

[0195]

Table 1

[0196] [Synthesis Example 16] Synthesis of Compound (A-13) for Forming Metal-Containing Film Under a nitrogen atmosphere, 14.2 g of titanium(IV) tetraisopropoxide (M2) was dissolved in 25.5 g of a PGMEA / PGME (weight ratio 70 / 30) solution, and while stirring, the reaction temperature was raised to 50 °C, and 9.0 g of compound H1 was added dropwise into the solution. After the addition, the reaction temperature was set to 60 °C and stirring was continued for 2 hours. Next, a mixture in which 30.2 g of compound G4 was suspended in 22.0 g of a PGMEA / PGME (weight ratio 70 / 30) solution was added to the reaction system, and stirring was continued for 1 hour while maintaining the reaction temperature at 60 °C. After cooling to room temperature, the obtained reaction solution was filtered through a 0.45 μm PTFE filter to obtain a PGMEA / PGME solution of the compound (A-13) for forming a metal-containing film. The concentration of components other than the solvent in the solution was 20% by mass.

[0197] [Synthesis Examples 17-18] Synthesis of Compounds (A-14) to (A-15) Compounds (A-14) to (A-15) shown in Table 2 were obtained under the same reaction conditions as in Synthesis Example 16, except that the above metal source M, the above compound group G, and the above compound group H were used in the charged amounts shown in Table 2.

[0198]

Table 2

[0199] [Synthesis Example 19] Synthesis of Compound (A-16) for Forming a Metal-Containing Film Under a nitrogen atmosphere, while stirring, a solution of 0.68 g of deionized water in 27.5 g of n-butanol was added dropwise to 20.5 g of an n-butanol solution of 14.2 g of titanium(IV) tetraisopropoxide (M2) at room temperature over 2 hours. 15.1 g of compound (G4) was added to the obtained solution, and the mixture was stirred at room temperature for 30 minutes. This solution was concentrated under reduced pressure at 30 °C, then further heated to 60 °C, and heating was continued under reduced pressure until no distillate was produced. When no distillate was observed, 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 compound (A-16) for forming a metal-containing film. The concentration of components other than the solvent in the solution was 19% by mass.

[0200] [Synthesis Examples 20 - 21] Synthesis of Compounds (A - 17) - (A - 18) Compounds (A - 17) - (A - 18) shown in Table 3 were obtained under the same reaction conditions as in Synthesis Example 19, except that the above metal source M and the above compound group G were used in the charged amounts shown in Table 3.

[0201] [Table 3]

[0202] [Preparation of Composition for Forming Metal - Containing Film] The cross - linking agent and the acid generator used for the preparation of the composition for forming a metal - containing film are shown below.

[0203] [Cross - Linking Agents XL - 1 - XL - 2)] The cross - linking agents (XL - 1) - (XL - 2) used in the composition for forming a metal - containing film are shown below. [Chemical Formula]

[0204] [Acid Generator (D - 1)] The acid generator (D - 1) used in the composition for forming a metal - containing film is shown below. [Chemical Formula]

[0205] [Preparation Example 1] Preparation of Composition for Forming Metal - Containing Film (UDL - 1) The compound (A - 1) for forming a metal - containing film was dissolved in a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) at the ratio shown in Table 4, and filtered through a 0.02 - μm membrane filter to prepare a composition for forming a metal - containing film (UDL - 1).

[0206] [Preparation Examples 2 - 24] Preparation of Compositions for Forming Metal - Containing Films (UDL - 2 - 21), Compositions for Forming Metal - Containing Films for Comparative Examples (Comparative Example UDL - 1 - 3) The respective chemical solutions were prepared in the same manner as UDL-1, except that the types and contents of the respective components were as shown in Table 4. In Table 4, "-" indicates that the corresponding component was not used. Ethylene glycol dibenzyl ether with a boiling point of 364 °C was used as the high-boiling solvent (F-1).

[0207] [Table 4]

[0208] [Examples 1-1 to 1-21, Comparative Examples 1-1 to 1-3] Patterning test 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. Next, the metal-containing film-forming compositions UDL-1 to 21 and Comparative Example UDL-1 to 3 prepared above were spin-coated on the Si substrate and heated at 250 °C for 60 seconds to fabricate a metal-containing film with a film thickness of 20 nm.

[0209] Subsequently, a resist material in which the following components were dissolved at the ratios shown in Table 5 was spin-coated on the metal-containing film, and pre-baked at 105 °C for 60 seconds using a hot plate to fabricate a resist film with a film thickness of 60 nm. This was exposed using an EUV scanner NXE3300 (NA 0.33, σ 0.9 / 0.6, quadrupole illumination, mask with a hole pattern having a wafer size pitch of 46 nm and a +20% bias) manufactured by ASML, PEB was performed on a hot plate at 100 °C for 60 seconds, and development was carried out with a 2.38 mass% TMAH aqueous solution for 30 seconds to obtain a hole pattern with a size of 23 nm.

[0210] Using a length-measuring SEM (CG5000) manufactured by Hitachi High-Technologies Corporation, the exposure dose when a hole size of 23 nm was formed was measured and taken as the sensitivity. Also, the sizes of 50 holes at this time were measured to obtain the size variation (CDU, 3σ). The results are shown in Table 6.

[0211] [Chemical formula]

[0212]

Chem.

[0213] ·Surfactant: FC-4430 manufactured by 3M

[0214]

Table 5

[0215]

Table 6

[0216] From the results shown in Table 6, it can be seen that when a metal-containing film containing a ligand substituted with a halogen atom, which is formed using the metal-containing film-forming composition containing the metal-containing film-forming compound of the present invention, is used as a resist intermediate film, a pattern can be formed with high sensitivity without deterioration of CDU (Examples 1-1 to 1-21). From this, it can be seen that the above resist intermediate film can contribute to the improvement of sensitivity while maintaining the LWR of the upper-layer resist. In particular, it was found that when a metal-containing film containing a ligand containing an iodine atom is used as a resist intermediate film, a pattern can be formed with high sensitivity (Examples 1-4 and 1-12).

[0217] When a resist intermediate film formed using a metal-containing film-forming composition containing a metal-containing film-forming compound that does not contain a crosslinkable group in the ligand is used, the CDU is comparable to that of the examples, but the sensitivity is poor (Comparative Examples 1-1 and 1-3). It is presumed that the heat resistance is insufficient because no organic crosslinking occurs between the ligands, and the ligand containing a halogen atom is thermally decomposed during baking. When a resist intermediate film formed using a metal-containing film-forming composition containing a metal-containing film-forming compound that does not contain a halogen atom is used, the CDU is comparable to that of the examples, but the sensitivity is poor (Comparative Example 1-2).

[0218] As described above, the present invention can break the trade-off relationship between sensitivity and LWR, and can form a resist underlayer film or intermediate film that can contribute to improving the sensitivity while maintaining the LWR of the upper-layer resist. Therefore, it has high utility value in the field of EUV lithography.

[0219] This specification includes the following inventions.

[0220] [1]: A metal-containing film-forming compound, wherein the metal-containing film-forming compound includes at least one metal atom (a) selected from the group consisting of Ti, Zr, and Hf, and a ligand that coordinates to the metal atom (a), and the ligand is substituted with a halogen atom, contains a carboxy group, and is derived from a compound (b) having 1 to 50 carbon atoms containing one or more crosslinkable groups selected from a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyloxy group, an epoxy group, an oxetanyl group, and a nitrile group. A metal-containing film-forming compound characterized by that.

[0221] [2]: The metal-containing film-forming compound according to [1] above, wherein the ligand is derived from a compound represented by the following formula (1). [Chemical formula] (In the above formula, R ais a monovalent organic group having 1 to 20 carbon atoms, one or more crosslinkable groups selected from a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyloxy group, an epoxy group, an oxetanyl group, and a nitrile group, and one or more halogen atoms, X m1 is a divalent organic group having 1 to 20 carbon atoms, and m1 is 0 or 1.)

[0222] [3]: The compound represented by the general formula (1) contains at least one aromatic ring, heteroaromatic ring, and alicyclic structure, and the compound for forming a metal-containing film according to the above [2].

[0223] [4]: R in the general formula (1) a has a structure represented by the following formula (1-A), and the compound for forming a metal-containing film according to the above [2] or [3].

Chemical formula

[0224] [5]: X of the general formula (1) m1 contains one or more carbonyl groups, and the compound for forming a metal-containing film according to any of the above [2] to [4].

[0225] [6]: The metal-containing film-forming compound further contains a ligand (c) derived from a silicon compound represented by the following general formula (2), and is the metal-containing film-forming compound according to any one of [1] to [5] above. [Chemical formula] (In the above general formula (2), R 3A , R 3B and R 3C are each an organic group having 1 to 30 carbon atoms with a cross-linking group having any of 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, or an aryl group having 1 to 20 carbon atoms, and are each selected from any of the organic groups.) [Chemical formula] (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 site.)

[0226] [7]: The metal-containing film-forming compound is a reaction product of a metal-containing compound containing at least one selected from a metal compound represented by the following formula (3), and a hydrolyzate, condensate, and hydrolyzate condensate of the metal compound represented by the following formula (3), and the compound represented by the formula (1), and is the metal-containing film-forming compound according to any one of [2] to [5] above. [Chemical formula] (In the formula, M is any one of Ti, Zr, and Hf. L is either a monodentate ligand or a multidentate ligand having 1 to 30 carbon atoms, and X is a hydrolyzable group selected from a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, and -NR a R b . R a and R b are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. a + b = 2 to 4, and a and b are integers from 0 to 4.)

[0227] [8]: The compound represented by the general formula (1) is a compound for forming a metal-containing film according to any one of [2] to [5] above, characterized in that it contains one or more fluorine atoms.

[0228] [9]: The compound represented by the general formula (1) is a compound for forming a metal-containing film according to any one of [2] to [5] above, characterized in that it contains one or more chlorine atoms.

[0229]

[10] : The compound represented by the general formula (1) is a compound for forming a metal-containing film according to any one of [2] to [5] above, characterized in that it contains one or more bromine atoms.

[0230]

[11] : The compound represented by the general formula (1) is a compound for forming a metal-containing film according to any one of [2] to [5] above, characterized in that it contains one or more iodine atoms.

[0231]

[12] : A composition for forming a metal-containing film that functions as a resist underlayer film material or a resist intermediate film material used in semiconductor manufacturing, comprising (A) a compound for forming a metal-containing film according to any one of [1] to

[11] above, and (B) an organic solvent.

[0232]

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

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

[0233]

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

[12] or

[13] above, characterized in that 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 ((B') high-boiling solvents) having a boiling point of 180°C or higher.

[0234]

[15] : A method for forming a pattern on a substrate to be processed, comprising: (I-1) a step of forming a metal-containing film by applying the composition for forming a metal-containing film according to any one of

[12] to

[14] on the substrate to be processed and then performing heat treatment; (I-2) a step of forming a resist upper layer film on the metal-containing film using a photoresist material; (I-3) a step of forming a pattern on the resist upper layer film by performing pattern exposure on the resist upper layer film and then developing it with a developer; (I-4) a step of transferring the pattern to the metal-containing film by dry etching using the resist upper layer film with the pattern formed thereon as a mask; and (I-5) a step of processing the substrate to be processed using the metal-containing film with the pattern formed thereon as a mask to form a pattern on the substrate to be processed. A pattern forming method characterized by comprising the above steps.

[0235]

[16] : A method for forming a pattern on a substrate to be processed, comprising: (II-1) a step of forming an organic resist lower layer film on the substrate to be processed; (II-2) a step of forming a metal-containing film by applying the composition for forming a metal-containing film according to any one of

[12] to

[14] on the organic resist lower layer film and then performing heat treatment; (II-3) a step of forming a resist upper layer film on the metal-containing film using a photoresist material; (II-4) a step of forming a pattern on the resist upper layer film by performing pattern exposure on the resist upper layer film and then developing it with a developer; (II-5) a step of transferring the pattern to the metal-containing film by dry etching using the resist upper layer film with the pattern formed thereon as a mask; (II-6) a step of transferring the pattern to the organic resist lower layer film by dry etching using the metal-containing film with the pattern transferred thereon as a mask; and (II-7) a step of processing the substrate to be processed using the organic resist lower layer film with the pattern formed thereon as a mask to form a pattern on the substrate to be processed. A pattern forming method characterized by comprising the above steps.

[0236]

[17] : A method for forming a pattern on a substrate to be processed, comprising: (III-1) a step of forming a metal-containing film by applying the composition for forming a metal-containing film according to any one of

[12] to

[14] on the substrate to be processed and then performing heat treatment; (III-2) a step of forming an inorganic hard mask intermediate film selected from a silicon-containing resist intermediate film, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film; (III-3) a step of forming an organic thin film on the inorganic hard mask intermediate film; (III-4) a step of forming an upper resist film using a photoresist material on the organic thin film; (III-5) a step of performing pattern exposure on the upper resist film and then developing it with a developer to form a pattern on the upper resist film; (III-6) a step of transferring the pattern to the organic thin film and the inorganic hard mask intermediate film by dry etching using the upper resist film with the pattern as a mask; (III-7) a step of transferring the pattern to the metal-containing film by dry etching using the inorganic hard mask intermediate film with the pattern as a mask; and (III-8) a step of processing the substrate to be processed using the metal-containing film with the pattern as a mask to form a pattern on the substrate to be processed. A pattern forming method characterized by comprising these steps.

[0237]

[18] : A method for forming a pattern on a substrate to be processed, comprising: (IV-1) a step of forming a metal-containing film by applying the composition for forming a metal-containing film according to any one of

[12] to

[14] on the substrate to be processed and then performing heat treatment; (IV-2) a step of forming an organic intermediate film on the metal-containing film; (IV-3) a step of forming 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 on the organic intermediate film; (IV-4) a step of forming a resist upper layer film using a photoresist material on the silicon-containing resist intermediate film or the organic thin film; (IV-5) a step of performing pattern exposure on the resist upper layer film and then developing with a developer to form a pattern on the resist upper layer film; (IV-6) a step of 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 using the resist upper layer film having the pattern as a mask; (IV-7) a step of transferring the pattern to the organic intermediate film by dry etching using the silicon-containing resist intermediate film or the inorganic hard mask intermediate film having the pattern as a mask; (IV-8) a step of transferring the pattern to the metal-containing film by dry etching using the organic intermediate film as a mask; and (IV-9) a step of processing the substrate to be processed using the metal-containing film having the pattern as a mask to form a pattern on the substrate to be processed. A pattern forming method characterized by comprising the above steps.

[0238]

[19] : The pattern forming method according to

[15] , characterized in that in the step (I-3), the pattern exposure is performed using EUV light.

[0239]

[20] : The pattern forming method according to

[16] , characterized in that in the step (II-4), the pattern exposure is performed using EUV light.

[0240]

[21] : The pattern forming method according to

[17] , characterized in that in the step (III-5), the pattern exposure is performed using EUV light.

[0241]

[22] The pattern forming method according to

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

[0242] Note that the present invention is not limited to the above-described embodiments. The above-described embodiments are examples, and any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits the same operational effects is included in the technical scope of the present invention.

Explanation of Reference Numerals

[0243] 1... Substrate to be processed, 1a... Pattern, 2... Organic resist lower layer film 2a... Organic resist lower layer film pattern, 3... Metal-containing film, 3a... Metal-containing film pattern 4... Resist upper layer film, 4a... Resist upper layer film pattern, 5... Mask, P... Exposure

Claims

1. A compound for forming a metal-containing film, wherein 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 ligand coordinated to the metal atom (a), and the ligand is substituted with a halogen atom, contains a carboxy group, and is derived from a compound (b) having 1 to 50 carbon atoms and containing one or more crosslinkable groups selected from a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyloxy group, an epoxy group, an oxetanyl group, and a nitrile group. A compound for forming a metal-containing film characterized by the above.

2. The compound for forming a metal-containing film according to claim 1, wherein the ligand is derived from a compound represented by the following formula (1). 【Chemical 1】 (In the above formula, R ａ is a monovalent organic group having 1 to 20 carbon atoms, which has one or more crosslinkable groups selected from a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyloxy group, an epoxy group, an oxetanyl group, and a nitrile group, and one or more halogen atoms, X ｍ１ is a divalent organic group having 1 to 20 carbon atoms, and m1 is 0 or 1.)

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

4. R in the general formula (1) ａ The compound for forming a metal-containing film according to claim 2, wherein R in the general formula (1) has a structure represented by the following formula (1-A). 【Chemical 2】 (In the above formula, X １ is a halogen atom or a monovalent organic group having 1 to 10 carbon atoms containing a halogen 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 ｘ is a monovalent organic group having 2 to 20 carbon atoms containing a crosslinkable group selected from a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a propargyl group, a propargyloxy group, an epoxy group, an oxetanyl group, and a nitrile group, 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, and a hydroxyl group, n １ is 1 to 5, n ２ is 1 to 4, n ３ is 0 to 2, and * is the bonding part with X ｍ１ .)

5. X of the general formula (1) ｍ１ The compound for forming a metal-containing film according to claim 2, wherein X contains one or more carbonyl groups.

6. The compound for forming a metal-containing film according to claim 1, wherein the compound for forming a metal-containing film further contains a ligand (c) derived from a silicon compound represented by the following general formula (2). 【Chemical Formula 3】 (In the above general formula (2), R ３Ａ , R ３Ｂ and R ３Ｃ is any one of organic groups having 1 to 30 carbon atoms and having a crosslinking group of any of 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.) 【Chemical Formula 4】 (In the above general formulas (c-1) to (c-3), R ３ 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.)

7. The compound for forming a metal-containing film according to claim 2, wherein the compound for forming a metal-containing film is a metal-containing compound containing one or more selected from a metal compound represented by the following formula (3), and a hydrolyzate, a condensate, and a hydrolyzed condensate of the metal compound represented by the following formula (3), and is a reaction product of the compound represented by the formula (1). 【Chemical Formula 5】 (In the formula, M is any one of Ti, Zr, and Hf. L is either a monodentate ligand or a multidentate ligand having 1 to 30 carbon atoms, and X is a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, -NR a R b is a hydrolyzable group selected from. 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.)

8. The compound for forming a metal-containing film according to claim 2, wherein the compound represented by the general formula (1) contains one or more fluorine atoms.

9. The compound for forming a metal-containing film according to claim 2, wherein the compound represented by the general formula (1) contains one or more chlorine atoms.

10. The compound for forming a metal-containing film according to claim 2, wherein the compound represented by the general formula (1) contains one or more bromine atoms.

11. The compound for forming a metal-containing film according to claim 2, wherein the compound represented by the general formula (1) contains one or more iodine atoms.

12. A composition for forming a metal-containing film that functions as a resist underlayer film material or a resist intermediate film material used in semiconductor manufacturing, (A) A compound for forming a metal-containing film according to any one of claims 1 to 11, and (B) an organic solvent characterized by containing the same, a composition for forming a metal-containing film.

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

14. The composition for forming a metal-containing film according to claim 12, characterized in that 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 ((B') high-boiling solvent) having a boiling point of 180°C or higher.

15. A method for forming a pattern on a substrate to be processed, comprising: (I-1) A step of forming a metal-containing film by applying the composition for forming a metal-containing film according to claim 12 on the substrate to be processed and then performing heat treatment; (I-2) A step of forming a resist upper layer film on the metal-containing film using a photoresist material; (I-3) A step of forming a pattern on the resist upper layer film by pattern exposure and then developing with a developer; (I-4) A step of transferring the pattern to the metal-containing film by dry etching using the resist upper layer film having the pattern as a mask, and (I-5) A step of processing the substrate to be processed using the metal-containing film having the pattern as a mask to form a pattern on the substrate to be processed characterized by having the same, a pattern forming method.

16. A method for forming a pattern on a substrate to be processed, comprising: (II-1) A step of forming an organic resist lower layer film on the substrate to be processed; (II-2) A step of forming a metal-containing film by applying the composition for forming a metal-containing film according to claim 12 on the organic resist lower layer film and then performing heat treatment; (II-3) A step of forming a resist upper layer film on the metal-containing film using a photoresist material; (II-4) A step of forming a pattern on the resist upper layer film by pattern exposure and then developing with a developer; (II-5) A step of transferring the pattern to the metal-containing film by dry etching using the resist upper layer film having the pattern as a mask; (II-6) A step of transferring the pattern to the organic resist lower layer film by dry etching using the metal-containing film having the pattern transferred as a mask, and Step (II-7): Using the organic resist underlayer film on which the pattern is formed as a mask, processing the substrate to be processed to form a pattern on the substrate to be processed A pattern forming method characterized by comprising the above steps. **Claim 17** A method for forming a pattern on a substrate to be processed, comprising: Step (III-1): Forming a metal-containing film by applying the composition for forming a metal-containing film according to claim 12 on the substrate to be processed and then performing a heat treatment; Step (III-2): Forming an inorganic hard mask intermediate film selected from a silicon-containing resist intermediate film, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film; Step (III-3): Forming an organic thin film on the inorganic hard mask intermediate film; Step (III-4): Forming a resist upper layer film using a photoresist material on the organic thin film; Step (III-5): After pattern-exposing the resist upper layer film, developing it with a developer to form a pattern on the resist upper layer film; Step (III-6): Using the resist upper layer film on which the pattern is formed as a mask, transferring the pattern to the organic thin film and the inorganic hard mask intermediate film by dry etching; Step (III-7): Using the inorganic hard mask intermediate film onto which the pattern is transferred as a mask, transferring the pattern to the metal-containing film by dry etching; and Step (III-8): Using the metal-containing film on which the pattern is formed as a mask, processing the substrate to be processed to form a pattern on the substrate to be processed A pattern forming method characterized by comprising the above steps. **Claim 18** A method for forming a pattern on a substrate to be processed, comprising: Step (IV-1): Forming a metal-containing film by applying the composition for forming a metal-containing film according to claim 12 on the substrate to be processed and then performing a heat treatment; Step (IV-2): Forming an organic intermediate film on the metal-containing film; Step (IV-3): Forming 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 on the organic intermediate film; Step (IV-4): Forming a resist upper layer film using a photoresist material on the silicon-containing resist intermediate film or the organic thin film; Step (IV-5): After pattern-exposing the resist upper layer film, developing it with a developer to form a pattern on the resist upper layer film; (IV-6) A step of transferring a pattern to the silicon-containing resist intermediate film, the organic thin film, and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern is formed as a mask; (IV-7) A step of transferring a pattern to the organic intermediate film by dry etching using the silicon-containing resist intermediate film or the inorganic hard mask intermediate film on which the pattern is transferred as a mask; (IV-8) A step of transferring a pattern to the metal-containing film by dry etching using the organic intermediate film as a mask, and (IV-9) A step of processing the substrate to be processed using the metal-containing film on which the pattern is formed as a mask to form a pattern on the substrate to be processed A pattern forming method, characterized by comprising the above steps.

19. The pattern forming method according to claim 15, wherein in the step (I-3), the pattern exposure is performed using EUV light.

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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