TW201841998A - Composition for silicon-containing-film formation, silicon-containing film, pattern formation method, and polysiloxane - Google Patents

Abstract

The purpose of the present invention is to provide: a composition for silicon-containing-film formation comprises a polysiloxane having a group represented by formula (1) and a solvent. In formula (1), L is a single bond or a C1-20 (n+1)-valent organic group, E is a group represented by formula (2-1) or (2-2), Y1 is an (un)substituted C6-20 aryl group or a C1-20 monovalent aliphatic hydrocarbon group in which a hydrogen atom has been replaced with an electron-attracting group, and Y2 is an (un)substituted C6-20 arylenediyl group or a C1-20 divalent aliphatic hydrocarbon group in which a hydrogen atom has been replaced with an electron-attracting group.

Description

Composition for forming ruthenium-containing film, ruthenium-containing film, pattern formation method, and polyoxyalkylene oxide

The present invention relates to a composition for forming a ruthenium-containing film, a ruthenium-containing film, a pattern formation method, and a polyoxyalkylene.

In the formation of a pattern of a semiconductor element or the like, a resist process is used, that is, exposure and development are performed on a resist film laminated on a substrate to be processed via an organic antireflection film and a ruthenium containing film. The resist pattern is etched as a mask. In recent years, as the resist pattern is miniaturized, the collapse of the resist pattern and the decrease in the etching selectivity of the mask pattern have become problems. Here, a material for a ruthenium-containing film which improves etching selectivity of a resist pattern or an etching pattern of a mask pattern, and a method of forming a pattern on a substrate using the material for a ruthenium-containing film have been studied. (Refer to Japanese Patent Laid-Open No. 2004-310019 and International Publication No. 2012/039337). [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-310019 [Patent Document 2] International Publication No. 2012/039337

[Problems to be Solved by the Invention] However, if the refinement of the resist pattern is 40 nm or less in line width, the above-described ruthenium-containing film cannot satisfy these requirements. In addition, when the ruthenium-containing film is removed by plasma etching by a fluorine-based gas or the like after the resist pattern is formed as a mask, the substrate to be processed is damaged. The removal of the ruthenium containing film must be improved.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a composition for forming a ruthenium-containing film, a ruthenium-containing film, a pattern formation method, and a polysiloxane, which can form a fluorine-maintaining composition. A ruthenium-containing film excellent in etching removability by gas and excellent in suppressing collapse resistance of a resist pattern. [Means for solving the problem]

In order to solve the problem, the invention is a composition for forming a ruthenium-containing film, which comprises a polysiloxane having a group represented by the following formula (1) and a solvent. [Chemical 1] (In the formula (1), L is a single bond or an (n+1)-valent organic group having 1 to 20 carbon atoms. E is a group represented by the following formula (2-1) or (2-2). n is an integer of 1 to 3. When n is 2 or more, L is an organic group, and a plurality of E are the same or different. * indicates a site bonded to a ruthenium atom in the polysiloxane. ] (In the formula (2-1), R ¹ is a single bond or a divalent organic group having ¹ to 20 carbon atoms. Y ¹ is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or at least one hydrogen atom A monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms substituted by an electron-donating group. In the formula (2-2), R ² is a monovalent organic group having 1 to 20 carbon atoms. Y ² is substituted or unsubstituted. a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms substituted with an alkyl group having 6 to 20 carbon atoms or at least one hydrogen atom via an electron withdrawing group)

Another invention to solve the above problems is a ruthenium-containing film formed of the ruthenium-containing film-forming composition.

According to still another aspect of the invention, there is provided a pattern forming method comprising: a step of forming a ruthenium-containing film on an upper side of a substrate by application of the composition for forming a ruthenium-containing film; The step of forming a pattern on the ruthenium film.

Still another invention to solve the above problems is a polysiloxane having a group represented by the formula (1). [Effects of the Invention]

According to the ruthenium-containing film-forming composition and the pattern forming method of the present invention, it is possible to form a ruthenium-containing film which is excellent in the etch-eliminability by the fluorine-based gas and has excellent collapse resistance of the resist pattern, and can form a confrontation. The ruthenium-containing film which is excellent in the resistance of the alkaline developing solution in the etchant pattern forming step and excellent in the peeling property by the alkaline hydrogen peroxide water. Further, the composition for forming a ruthenium-containing film of the present invention is also excellent in storage stability. The ruthenium-containing film of the present invention maintains the etching removability by the fluorine-based gas, and is excellent in the collapse suppressing property of the resist pattern, and is excellent in the resistance to the alkaline developing solution in the resist pattern forming step and is alkaline. Excellent in peeling properties due to hydrogen peroxide water. The polyoxyalkylene of the present invention can be preferably used as the polyoxymethane component of the composition for forming a ruthenium-containing film. Therefore, these can be preferably used for a multilayer resist process, and can be preferably used for the manufacture of a semiconductor device in which further miniaturization is expected in the future.

Hereinafter, embodiments of the composition for forming a ruthenium-containing film of the present invention, a polysiloxane, a ruthenium-containing film, and a pattern formation method will be described.

<The composition for forming a ruthenium-containing film> The composition for forming a ruthenium-containing film contains a polysiloxane having a group represented by the formula (1) (hereinafter also referred to as "[A] polyoxane"), And solvent (hereinafter also referred to as "[B] solvent"). The composition for forming a ruthenium-containing film may contain an optional component insofar as the effects of the present invention are not impaired. Hereinafter, each component will be described.

<[A] Polyoxane> [A] Polyoxyalkylene is a polyoxyalkylene having a group represented by the following formula (1) (hereinafter also referred to as "base (I)").

[Chemical 3]

In the formula (1), L is a single bond or an (n+1)-valent organic group having 1 to 20 carbon atoms. E is a group represented by the following formula (2-1) or formula (2-2) (hereinafter, also referred to as "base (II-1) or group (II-2)"). n is an integer of 1-3. When n is 2 or more, L is an organic group, and a plurality of E are the same or different. * indicates a site bonded to a ruthenium atom in the polyoxyalkylene.

[Chemical 4]

In the formula (2-1), R ¹ is a single bond or a divalent organic group having 1 to 20 carbon atoms. Y ¹ is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms substituted with at least one hydrogen atom via an electron withdrawing group. In the formula (2-2), R ² is a monovalent organic group having 1 to 20 carbon atoms. Y ² is a substituted or unsubstituted divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which is substituted with an alkylene group having 6 to 20 carbon atoms or at least one hydrogen atom via an electron withdrawing group.

The composition for forming a ruthenium-containing film can form an etching removal property by maintaining a fluorine-based gas by containing [A] a polysiloxane and a solvent of [B], and is excellent in collapse suppressability of a resist pattern, and The antimony-containing film which is excellent in resistance to the alkaline developing solution in the resist pattern forming step and excellent in peeling property due to alkaline hydrogen peroxide water is further excellent in storage stability. The reason why the composition for forming a ruthenium-containing film has the above-described configuration and the above-described effects are not necessarily clear, but it can be estimated as follows. In other words, the [A] polysiloxane having the composition for forming a ruthenium film has a group (I) having a sulfonate structure in which an electron withdrawing group or the like is bonded. Since the sulfonate structure is bonded to an electron-donating group or the like, it is not easily cracked regardless of the temperature at normal temperature or heating. Therefore, the composition for forming a ruthenium-containing film is excellent in storage stability, and the formed ruthenium-containing film is excellent in resistance to an alkaline developer. Further, since the oxime ester structure is cleaved by alkaline hydrogen peroxide water to generate a sulfo group, the ruthenium-containing film is excellent in releasability due to alkaline hydrogen peroxide water.

[Base (I)] The (n+1)-valent organic group having 1 to 20 carbon atoms represented by L in the formula (1) includes (n+1) valence of 1 to 20 carbon atoms. a hydrocarbon group, a carbon-carbon group containing a divalent hetero atom-containing group (α), a part or all of a hydrogen atom possessed by the hydrocarbon group and the group (α), and a monovalent hetero atom-containing group Substituted bases, etc.

Examples of the (n+1)-valent hydrocarbon group having 1 to 20 carbon atoms include a (n+1)-valent chain hydrocarbon group having 1 to 20 carbon atoms and a (n+1)-valent carbon number of 3 to 20 carbon atoms. An alicyclic hydrocarbon group, an (n+1)-valent aromatic hydrocarbon group having 6 to 20 carbon atoms, or the like.

Examples of the (n+1)-valent chain hydrocarbon group having 1 to 20 carbon atoms include an alkane such as methane, ethane, propane or butane, an olefin such as ethylene, propylene or butylene, acetylene, propyne or butyne. A group obtained by removing two to four hydrogen atoms such as an alkyne or the like.

Examples of the (n+1)-valent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a saturated ring such as cyclopentane such as cyclopentane or cyclohexane, norbornane, adamantane or tricyclodecane. 2 to 4 of alicyclic unsaturated hydrocarbons such as alicyclic saturated hydrocarbons such as hydrocarbons, cycloolefins such as cyclopentene and cyclohexene, alicyclic unsaturated hydrocarbons such as bridged cyclic unsaturated hydrocarbons such as norbornene and tricyclodecene A base obtained by removing a hydrogen atom.

Examples of the (n+1)-valent aromatic hydrocarbon group having 6 to 20 carbon atoms include an aromatic hydrocarbon such as benzene, toluene, ethylbenzene, xylene, naphthalene, methylnaphthalene, anthracene or methyl anthracene. A hydrogen atom on one to four aromatic rings or a group in which two to four aromatic rings and a hydrogen atom on an alkyl group are removed.

Examples of the hetero atom constituting the group containing a divalent or monovalent hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a ruthenium atom, and a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the divalent hetero atom-containing group include -O-, -CO-, -S-, -CS-, and -NR'-, and a combination of two or more of these. R' is a hydrogen atom or a monovalent hydrocarbon group. Among these, -O- and -S- are preferred.

Examples of the group having a monovalent hetero atom include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a hydroxyl group, a carboxyl group, a cyano group, an amine group or a fluorenyl group. Among these, a halogen atom is preferred, and a fluorine atom is more preferred.

n as the formula (1) is preferably 1 or 2, more preferably 1.

The L is preferably a (n+1)-valent hydrocarbon group and a group containing a divalent hetero atom-containing group between the carbon-carbons of the hydrocarbon group, more preferably a (n+1)-valent chain hydrocarbon group or aroma. The group hydrocarbon group and the group containing a group containing a divalent hetero atom between the carbon and carbon of the hydrocarbon group. In the case where n is 1, as L, further preferably an alkanediyl group, a group containing -O- or -S- between carbon-carbons of an alkanediyl group, and an aromatic hydrocarbon diyl group, particularly preferably a methane diyl group, Ethane diyl, propane diyl, methane diyl fluorenyl methane diyl, methane diyl decyl ethane diyl, ethane diyl decyl ethane diyl, propane diyl fluorenyl methane diyl, propane diyl decyl ethane Diyl, methanediyloxymethanediyl, methanediyloxyethanediyl, ethanediyloxymethanediyl, ethanediyloxyethanediyl, propanediyloxymethane a base, a propane diyloxyethanediyl group, and a phenyldiyl group.

When L is a group containing a group containing a divalent hetero atom between carbon-carbons of a hydrocarbon group, the etching removeability by the fluorine-containing gas containing a ruthenium film can be further improved.

[Base (II-1)] The divalent organic group having 1 to 20 carbon atoms represented by R ¹ in the above formula (2-1) is, for example, an organic compound of the (n+1) valence of L described above. In the example, n is a group of 1 or the like.

As R ¹ , a single bond is preferred.

Examples of the aryl group in the substituted or unsubstituted aryl group having 6 to 20 carbon atoms represented by Y ¹ of the formula (2-1) include a phenyl group, a benzyl group, a tolyl group, and a xylene group. Base, naphthyl, anthracenyl and the like.

Examples of the substituent of the aryl group of Y ¹ include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a hydroxyl group, a cyano group, a nitro group, a decyl group, a decyloxy group, a hydrocarbon group, and an oxyhydrocarbyl group. Wait. Among these, from the viewpoint of electron pullability, a halogen atom, a cyano group, a nitro group, a fluorenyl group and a decyloxy group are preferred, and a halogen atom is more preferred, and a fluorine atom is preferred.

The substituted or unsubstituted aryl group having 6 to 20 carbon atoms of the Y ¹ is preferably a phenyl group, a naphthyl group, an anthranyl group, a fluorophenyl group, a chlorophenyl group, a trifluorophenyl group or a pentafluorobenzene. The group is preferably a phenyl group, a fluorophenyl group or a fluorobenzyl group, more preferably a phenyl group or a fluorophenyl group.

a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms substituted with at least one hydrogen atom represented by Y ¹ of the formula (2-1) via an electron withdrawing group (hereinafter, also referred to as "electron-based substituted fat" The aliphatic hydrocarbon group in the hydrocarbon group ") may, for example, be a (n+1)-valent chain hydrocarbon group having 1 to 20 carbon atoms as the L, and an (n+1)-valent alicyclic ring having 3 to 20 carbon atoms. In the exemplified hydrocarbon group, a group in which a hydrogen atom is added to a divalent group in which n is 1 is exemplified.

Examples of the electron withdrawing group in the aliphatic group-substituted aliphatic hydrocarbon group of Y ¹ include a halogen atom, a cyano group, a nitro group, a halogenated hydrocarbon group having 1 to 10 carbon atoms, and a -O having 1 to 10 carbon atoms. - a group having a -SO- group having 1 to 10 carbon atoms, a group having -SO ₂ - having 1 to 10 carbon atoms, a group having -CO- having 1 to 10 carbon atoms, and a carbon number of 1 to 10 A group having -COO- or the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the halogenated hydrocarbon group having 1 to 10 carbon atoms include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a trifluoroethyl group, a hexafluoroisopropyl group, and a pentafluoro-n-propyl group. A halogenated chain hydrocarbon group such as a hexafluoro-n-butyl group or the like.

Examples of the monovalent group having a carbon number of 1 to 10 and having a -O- group include an oxy group such as a methoxy group, a cyclohexyloxy group or a phenoxy group, a hydroxyaromatic hydrocarbon group such as a hydroxyphenyl group, a tetrahydrofuranyl group or the like. A cyclic ether group such as a hydropyranyl group or the like.

Examples of the monovalent group having a carbon number of 1 to 10 and having a -SO- group include a sulfonic acidoxy group such as a methylsulfonic acid group or a phenylsulfonic acid group, and a S-oxotetrahydrothiobenzene group. A cyclic sulfonic acid oxy group or the like.

As having 1 to 10 carbon atoms is -SO ₂ - group is, for example, a monovalent group include: methyl acyl sulfo, acyl and the like sulfo sulfo phenyl acyl hydrocarbyl, S- dioxo-tetrahydro-thiophenyl Such as a cyclic sulfonyl group and the like.

Examples of the monovalent group having a carbon number of 1 to 10 and having a -CO- group include a fluorenyl group such as a mercapto group, an ethenyl group or a benzamidine group, an oxocyclohexyl group or an oxoadamantyl group. Keto group and the like.

Examples of the monomethyl group having a carbon number of 1 to 10 and having a -COO- group include a decyloxy group such as a methyl methoxy group, an ethoxycarbonyl group or a benzyl methoxy group, a methoxycarbonyl group or a phenoxycarbonyl group. A group containing a lactone structure, such as a carbonyloxy hydrocarbon group, a butyrolactone-based group, a norbornane lactone-based group, or the like.

The electron-donating group is preferably a halogen atom, a cyano group, a halogenated hydrocarbon group having 1 to 10 carbon atoms, a group having -O- having 1 to 10 carbon atoms, and -SO- having 1 to 10 carbon atoms. a group having a -SO ₂ - group having 1 to 10 carbon atoms, a group having -CO- having 1 to 10 carbon atoms, and a group having -COO- having 1 to 10 carbon atoms, more preferably a fluorine atom or a chlorine atom. An atom, a cyano group, a fluorinated hydrocarbon group, an oxyhydrocarbyl group, a fluorenyl group, a carbonyloxy hydrocarbon group, and a sulfonyl hydrocarbon group, and more preferably a fluorine atom, a chlorine atom, a cyano group, a fluorinated alkyl group, an alkoxy group, an alkylcarbonyl group, The alkoxycarbonyl group and the alkylsulfonyl group are particularly preferably a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a methoxy group, an ethyl fluorenyl group, a methoxycarbonyl group or a methylsulfonyl group.

It is considered that when a fluorine atom is contained in the base (I) as an electron-donating group or the like, the ruthenium-containing film formed of [A] polysiloxane and the resist pattern formed on the upper side thereof, in particular, by alkali development The adhesion of the formed positive resist pattern is further improved, and the collapse inhibition property of the resist pattern is further improved. When the [A] polyoxyalkylene contains a fluorine atom, the etching removability by the fluorine-based gas is further improved. Further, when the [A] polyoxyalkylene contains a fluorine atom, the sensitivity of the radiation sensitive resin composition when Extreme Ultraviolet (EUV) is used can be improved.

The alkyl group represented by the following formula (4-1) and the like are exemplified as the electron-donating group-substituted aliphatic hydrocarbon group of Y ¹ .

[Chemical 5]

In the formula (4-1), R ⁴ to R ⁸ each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 18 carbon atoms or a monovalent electron-donating group. p is 0 or 1. However, when p is 0, at least one of R ⁶ to R ⁸ is an electron withdrawing group. When p is 1, at least one of R ⁴ to R ⁸ is an electron withdrawing group.

R ⁴ to R ^{8 are} preferably a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a methoxy group, a methoxycarbonyl group, a methylsulfonyl group or an ethoxy group.

As Y ¹ , an electron-donating group is preferably substituted for the aliphatic hydrocarbon group.

[Base (II-2)] The monovalent organic group having 1 to 20 carbon atoms represented by R ² in the formula (2-2), for example, may be exemplified as the (n+1)-valent organic group of the above-mentioned L. In the example, a group in which a hydrogen atom is added to a divalent organic group in which n is 1 is used. Among these, a monovalent hydrocarbon group is preferred, a monovalent chain hydrocarbon group is more preferred, and an alkyl group is further preferred, and a methyl group and an ethyl group are particularly preferred.

Examples of the substituted or unsubstituted aromatic hydrocarbon diyl group having 6 to 20 carbon atoms represented by Y ² of the above formula (2-2) include a benzenediyl group and a toluenediyl group. Xylene diyl, naphthalenediyl, anthracenyl and the like. Among these, a benzenediyl group is preferred.

Examples of the substituent of the aromatic hydrocarbon diradical group of Y ² include, for example, a substituent of the aryl group of Y ¹ . Among these, a halogen atom is preferred, and a fluorine atom is more preferred.

The alkyl group represented by the following formula (4-2) is exemplified as the electron-donating group-substituted aliphatic hydrocarbon group of Y ² .

[Chemical 6]

In the formula (4-2), R ⁹ to R ¹² each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 18 carbon atoms or a monovalent electron-donating group. R ¹³ is a single bond, a divalent hydrocarbon group having 1 to 18 carbon atoms or a divalent electron-donating group. q is 0 or 1. However, when q is 0, at least one of R ¹¹ to R ¹³ is an electron withdrawing group. When q is 1, at least one of R ⁹ to R ¹³ is an electron withdrawing group. ** indicates a site bonded to -O- in the formula (2-2).

R ⁹ to R ^{12 are} preferably a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a trifluoromethyl group, a cyano group, a methoxy group, a methoxycarbonyl group, a methylsulfonyl group or an ethoxy group.

As R ¹³ , a single bond is preferred.

As q, it is preferably 1.

As Y ² , a substituted or unsubstituted arene diyl group is preferred, and a substituted or unsubstituted phenyldiyl group is more preferred, and a phenyldiyl group and a fluorophenyldiyl group are further preferred.

[A] Polyoxyalkylene has a first structural unit represented by the formula (3) containing the above-mentioned group (I) (hereinafter also referred to as "structural unit (I)"). [A] Polyoxyalkylene preferably has a second structural unit (hereinafter also referred to as "structural unit (II)") represented by the following formula (5) in addition to the structural unit (I), and/or a later formula (3) The third structural unit (hereinafter also referred to as "structural unit (III)") may have a structure other than the structural unit (I) to the structural unit (III) without departing from the effects of the present invention. Other structural units. Hereinafter, each structural unit will be described.

[Structural unit (I)] The structural unit (I) is a structural unit represented by the following formula (3). The composition for forming a ruthenium-containing film has a structural unit (I) by [A] polyoxyalkylene, which can further improve resistance to an alkaline developer, collapse inhibition of a resist pattern, and alkaline hydrogen peroxide. Peelability and storage stability caused by water.

[Chemistry 7]

In the formula (3), Z is the group (I). R ³ is a monovalent organic group having 1 to 20 carbon atoms, a hydrogen atom or a hydroxyl group which does not contain -SO ₂ O-. m is an integer of 0 to 2. In the case where m is 2, the two R ^{3 are the} same or different.

The monovalent organic group having 1 to 20 carbon atoms which does not contain -SO ₂ O- represented by R ³ may, for example, be a monovalent organic group having 1 to 20 carbon atoms of R ² of the above formula (2-2). The same as the base.

As R ³ , an alkoxy group and a hydroxyl group are preferred.

As m, it is preferably 0 and 1, more preferably 0.

The monomer having a structural unit (I), for example, a compound having a group (II-1), a compound represented by the following formula (i-1-1) to (i-1-18) (hereinafter, The compound (i-1-1) to the compound (i-1-18), and the monomer having a group represented by the group (II-2) is exemplified by the following formula (i-2-1). The compound represented by the formula (i-2-3) (hereinafter also referred to as "compound (i-2-1) to the compound (i-2-3)").

[化8]

[Chemistry 9]

[化10]

In the formula (i-1-1) to the formula (i-1-18) and the formula (i-2-1) to the formula (i-2-3), R is a monovalent hydrocarbon group having 1 to 20 carbon atoms. .

The hydrocarbon group of R is preferably an alkyl group, more preferably a methyl group and an ethyl group.

The lower limit of the content ratio of the structural unit (I) is preferably 0.1 mol%, more preferably 1 mol%, and still more preferably 2 mol%, based on all structural units constituting the [A] polyoxyalkylene. More preferably, it is 5 mol%, and particularly preferably 8 mol%. The upper limit of the content ratio is preferably 80% by mole, more preferably 50% by mole, still more preferably 30% by mole, still more preferably 20% by mole. By setting the content ratio of the structural unit (I) to the above range, the composition for forming a ruthenium-containing film can further improve resistance to an alkaline developer, collapse inhibition of a resist pattern, and alkaline peroxidation. Peelability and storage stability caused by hydrogen water.

[Structural unit (II)] The structural unit (II) is a structural unit represented by the following formula (5). The composition for forming a ruthenium-containing film has the structural unit (II) by [A] polyoxyalkylene, and the etching resistance by the oxygen-containing gas containing the ruthenium film can be further improved.

[11]

The monomer which provides the structural unit (II) may, for example, be a tetraalkyl decane such as tetramethoxy decane such as tetramethoxy decane or tetraethoxy decane, tetrachloro decane or tetrabromodecane such as tetrabromodecane.

In the case where the [A] polyoxyalkylene has the structural unit (II), the lower limit of the content ratio of the structural unit (II) is preferably 1 mol with respect to all the structural units constituting the [A] polyoxyalkylene. The ear%, more preferably 10% by mole, and further preferably 30% by mole, more preferably 60% by mole. The upper limit of the content ratio is preferably 95% by mole, more preferably 90% by mole, still more preferably 85% by mole, still more preferably 80% by mole. By setting the content ratio of the structural unit (II) to the above range, the composition for forming a ruthenium-containing film can further improve the resistance to the alkaline developing solution and the etching resistance by the oxygen-based gas.

[Structural unit (III)] The structural unit (III) is a structural unit represented by the following formula (6). The composition for forming a ruthenium-containing film has a structural unit (III) by [A] polyoxyalkylene, and various characteristics of the ruthenium-containing film can be adjusted.

[化12]

In the formula (6), R ^A is a monovalent organic group having 1 to 20 carbon atoms which does not contain -SO ₂ O-. a is 1 or 2. In the case where a is 2, the two R ^{A are the} same or different.

The monovalent organic group having 1 to 20 carbon atoms which does not contain -SO ₂ O- represented by R ^A may, for example, be a monovalent organic group having 1 to 20 carbon atoms of R ² of the above formula (2-2). The same as the base. Among these, a hydrocarbon group is preferred, a chain hydrocarbon group and an aromatic hydrocarbon group are more preferred, and an alkyl group and an aryl group are preferred, and a methyl group, an ethyl group, a phenyl group and a naphthyl group are particularly preferred.

As a, it is preferably 1.

Examples of the monomer which provides the structural unit (III) include methyltrimethoxydecane, phenyltriethoxydecane, dimethyldimethoxydecane, diphenyldiethoxydecane, and methyl group. Phenyldimethoxydecane, cyclohexyltrichlorodecane, and the like.

In the case where the [A] polyoxyalkylene has the structural unit (III), the lower limit of the content ratio of the structural unit (III) is preferably 0.1 mol with respect to all structural units constituting the [A] polyoxyalkylene. The ear %, more preferably 1 mol%, and further preferably 8 mol%, particularly preferably 12 mol%. The upper limit of the content ratio is preferably 80 mol%, more preferably 50 mol%, still more preferably 40 mol%, and still more preferably 25 mol%.

[Other structural unit] [A] Polyoxyalkylene may have other structural units other than the structural unit (I) to the structural unit (III) as long as the effects of the present invention are not impaired. Examples of the other structural unit include a structural unit derived from a decane monomer containing a plurality of ruthenium atoms such as hexamethoxydioxane, bis(trimethoxydecyl)methane, or polydimethoxymethylcarbane. . In the case where the [A] polyoxyalkylene has other structural units, the upper limit of the content ratio of the other structural unit is preferably 10 mol%, more preferably 10 mol%, based on all structural units constituting the [A] polyoxyalkylene. Preferably, it is 5% by mole, and further preferably 2% by mole, and particularly preferably 5% by mole.

The lower limit of the content of the [A] polyoxane is preferably 50% by mass, more preferably 80% by mass, even more preferably 90% by mass, based on the total solid content of the composition for forming a ruthenium-containing film. Good is 95% by mass. The upper limit of the content is preferably 100% by mass, preferably 99% by mass, and more preferably 97% by mass. The total solid content of the composition for forming a ruthenium-containing film means the sum of components other than the solvent [B]. [A] The polyoxyalkylene may be contained alone or in combination of two or more.

The lower limit of the weight average molecular weight (Mw) of [A] polyoxyalkylene is preferably 1,000, more preferably 1,300, still more preferably 1,500, still more preferably 1,700. The upper limit of the Mw is preferably 100,000, more preferably 20,000, still more preferably 7,000, and still more preferably 3,000.

The Mw of [A] polyoxane in this specification is a gel permeation chromatography (GPC) column of Tosoh Corporation (2 "G2000HXL", "G3000HXL" and 1" G4000HXL"1), under the conditions of flow rate: 1.0 mL/min, dissolution solvent: tetrahydrofuran, column temperature: 40 ° C, by gel permeation chromatography using monodisperse polystyrene as a standard (detector: The value measured by the differential refractometer.

[A] Polyoxyalkylene can be obtained by a method of hydrolyzing and condensing a hydrolyzable decane monomer corresponding to each of the structural units. It is considered that each hydrolyzable decane monomer is introduced into the polyoxyalkylene by a hydrolysis condensation reaction, and the structural unit (I) to structural unit (III) and other components in the synthesized [A] polyaluminoxane are synthesized. The ratio of the content ratio of the structural unit to the amount of each monomer compound used in the synthesis reaction is usually equal.

<[B] Solvent> The composition for forming a ruthenium-containing film contains a [B] solvent. Examples of the [B] solvent include an alcohol-based solvent, a ketone-based solvent, an ether-based solvent, an ester-based solvent, a nitrogen-containing solvent, and water. [B] The solvent may be used singly or in combination of two or more.

Examples of the alcohol-based solvent include monool-based solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol; ethylene glycol, 1,2-propanediol, diethylene glycol, and two. A polyol-based solvent such as propylene glycol.

Examples of the ketone-based solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-isobutyl ketone, and cyclohexanone.

Examples of the ether solvent include diethyl ether, diisopropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and propylene glycol. Monoethyl ether, propylene glycol monopropyl ether, tetrahydrofuran, and the like.

Examples of the ester-based solvent include ethyl acetate, γ-butyrolactone, n-butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and diethylene glycol monomethyl ether. Acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethyl propionate , n-butyl propionate, methyl lactate, ethyl lactate and the like.

Examples of the nitrogen-containing solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

Among these, an ether solvent and an ester solvent are preferred, and since it has excellent film formability, it is more preferably an ether solvent or an ester solvent having a diol structure.

Examples of the ether solvent and the ester solvent having a diol structure include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl acetate. Ether acetate and the like. Among these, propylene glycol monomethyl ether acetate is particularly preferred.

The lower limit of the content of the ether solvent and the ester solvent having a diol structure in the solvent of [B] is preferably 20% by mass, more preferably 60% by mass, still more preferably 90% by mass, and particularly preferably 100%. quality%.

The lower limit of the content of the [B] solvent in the composition for forming a ruthenium-containing film is preferably 80% by mass, more preferably 90% by mass, still more preferably 95% by mass. The upper limit of the content is preferably 99% by mass, and more preferably 98% by mass.

<Optional component> The composition for forming a ruthenium-containing film may contain an optional component such as a basic compound or an acid generator.

[Basic compound] Examples of the basic compound (including a base generator) include a compound having a basic amino group or a compound having a basic amine group by the action of an acid or heat (alkali) Producer). More specifically, an amine compound, a guanamine-containing compound, a urea compound, a nitrogen-containing heterocyclic compound, etc. which are an alkali generator are mentioned. When the basic compound is contained in the composition for forming a ruthenium-containing film, the composition for forming the ruthenium-containing film can be promoted, and the peeling property of the obtained ruthenium-containing film with respect to the acidic liquid can be further improved.

Examples of the amine compound include mono(cyclo)alkylamines, di(cyclo)alkylamines, tri(cyclo)alkylamines, substituted alkylanilines or derivatives thereof, and ethylene. Amine, N, N, N', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4' -diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis(4-aminophenyl)propane, 2-(3-Aminophenyl)-2-(4-aminophenyl)propane, 2-(4-aminophenyl)-2-(3-hydroxyphenyl)propane, 2-(4- Aminophenyl)-2-(4-hydroxyphenyl)propane, 1,4-bis(1-(4-aminophenyl)-1-methylethyl)benzene, 1,3-double (1 -(4-Aminophenyl)-1-methylethyl)benzene, bis(2-dimethylaminoethyl)ether, bis(2-diethylaminoethyl)ether, 1-( 2-hydroxyethyl)-2-imidazolidinone, 2-quinazolidone, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, N,N,N',N' 'N''-pentamethyldiethylenetriamine and the like.

Examples of the guanamine-containing compound include N-tert-butoxycarbonyl-4-hydroxypiperidine, N-tert-butoxycarbonyl-2-carboxy-4-hydroxypyrrolidine, and N- N-tert-butoxycarbonyl-containing amine compound such as tributoxycarbonyl-2-carboxypyrrolidine; N-third pentyloxycarbonyl-4-hydroxypiperidine and the like containing N-third pentyloxycarbonyl group Amine compound; N-(9-fluorenylmethoxycarbonyl)-containing amine compound such as N-(9-fluorenylmethoxycarbonyl) piperidine; formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, acetamide, benzamide, pyrrolidone, N-A Pyrrolidone, N-ethinyl-1-adamantylamine, and the like.

Examples of the urea compound include urea, methyl urea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, and 1,3. - Diphenylurea, tri-n-butylthiourea, and the like.

Examples of the nitrogen-containing heterocyclic compound include imidazoles, pyridines, piperazines, pyrazines, pyrazoles, pyridazines, quinazolines, anthracenes, pyrrolidines, piperidines, piperidines, and 3-mer (N-piperidinyl)-1,2-propanediol, morpholine, 4-methylmorpholine, 1-(4-morpholinyl)ethanol, 4-ethylmercaptomorpholine, 3-(N-morpholine Base)-1,2-propanediol, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, and the like.

In the present embodiment, among these, a mercapto group-containing compound and a nitrogen-containing heterocyclic compound are particularly preferable. As the guanamine-containing compound, an amine compound containing an N-tert-butoxycarbonyl group, an amine compound containing an N-third pentyloxycarbonyl group, and an N-(9-fluorenylmethoxycarbonyl group) are more preferable. An amine compound, preferably N-tertoxycarbonyl-4-hydroxypiperidine, N-tert-butoxycarbonyl-2-carboxy-4-hydroxypyrrolidine, N-tert-butoxy Carbonyl-2-carboxy-pyrrolidine, N-third pentyloxycarbonyl-4-hydroxypiperidine and N-(9-fluorenylmethoxycarbonyl)piperidine. As the nitrogen-containing heterocyclic compound, 3-(N-piperidinyl)-1,2-propanediol is preferred.

When the composition for forming a ruthenium-containing film contains a basic compound, the content of the basic compound relative to 100 parts by mass of the [A] polyoxane is preferably 0.01 parts by mass, more preferably 0.1 part by mass. The mass%, and more preferably 0.5 parts by mass, is particularly preferably 1 part by mass. The upper limit of the content is preferably 20 parts by mass, more preferably 10 parts by mass, and still more preferably 5 parts by mass.

[Acid Generator] The acid generator is a compound which generates an acid by irradiation and/or heating of ultraviolet light. When the composition for forming a ruthenium-containing film contains an acid generator, the curing can be promoted, and as a result, the strength of the ruthenium-containing film can be further improved, and solvent resistance or oxygen etching resistance can be improved. The acid generators may be used alone or in combination of two or more.

Examples of the acid generator include an onium salt compound and an N-sulfonoxyquinone imine compound.

Examples of the onium salt compound include an onium salt, a tetrahydrothiophene salt, an onium salt, and an ammonium salt.

Examples of the onium salt include the onium salt described in paragraph [0110] of JP-A-2014-037386, and more specifically, triphenylsulfonium trifluoromethanesulfonate and triphenylsulfonium nonafluoride. - n-butanesulfonate, triphenylsulfonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyldiphenylphosphonium Trifluoromethanesulfonate and the like.

Examples of the tetrahydrothiophene sulfonium salt include a tetrahydrothiophene sulfonium salt described in paragraph [0111] of JP-A-2014-037386, and more specifically, 1-(4-n-butoxynaphthalene- 1-yl)tetrahydrothiophene trifluoromethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene nonafluoro-n-butanesulfonate, 1-(4-n-butyl) Oxynaphthalen-1-yl)tetrahydrothiophene 2-cyclobi[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate and the like.

Examples of the onium salt include the onium salt described in paragraph [0112] of JP-A-2014-037386, and more specifically, diphenylsulfonium trifluoromethanesulfonate, diphenylsulfonium nonafluoride-positive Butane sulfonate, diphenyl hydrazine 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis(4-t-butylphenyl)fluorene Nonafluoro-n-butanesulfonate and the like.

Examples of the ammonium salt include trimethylammonium nonafluoro-n-butylsulfonate and triethylammonium nonafluoro-n-butanesulfonate.

The N-sulfonyloxyimine compound described in paragraph [0113] of JP-A-2014-037386, and more specifically, N: -(Trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(nonafluoro-n-butylsulfonyloxy)bicyclo[2.2.1 G-8-ene-2,3-dicarboxy quinone imine, N-(2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, and the like.

In the case where the composition for forming a ruthenium-containing film contains an acid generator, the content of the acid generator relative to 100 parts by mass of the [A] polyoxane is preferably 0.01 parts by mass, more preferably 0.1 part by mass. The mass%, and more preferably 0.5 parts by mass, is particularly preferably 1 part by mass. The upper limit of the content is preferably 20 parts by mass, more preferably 10 parts by mass, and still more preferably 5 parts by mass.

The composition for forming a ruthenium-containing film may contain other optional components in addition to the basic compound and the acid generator. Examples of other optional components include a surfactant, a radical generator, colloidal cerium oxide, colloidal alumina, and an organic polymer. In the case where the composition for forming a ruthenium-containing film contains other optional components, the upper limit of the content is preferably 2 parts by mass, more preferably 1 part by mass, per 100 parts by mass of the [A] polysiloxane.

<Method for Producing Composition Containing Antimony Film> The method for preparing the composition for forming a hafnium film is not particularly limited, and can be prepared, for example, by [A] polyoxane, [B] solvent, and The optional components are mixed in a predetermined ratio as needed, and it is preferred to filter the resulting mixed solution with a filter having a pore size of 0.2 μm.

The lower limit of the solid content concentration of the composition for forming a ruthenium-containing film is preferably 0.01% by mass, more preferably 0.05% by mass, still more preferably 0.1% by mass, still more preferably 0.2% by mass. The upper limit of the solid content concentration is preferably 20% by mass, more preferably 10% by mass, still more preferably 5% by mass, and particularly preferably 3% by mass. The solid content concentration of the composition for forming a ruthenium-containing film is a value (% by mass) calculated by calcining the composition for forming a ruthenium-containing film at 250 ° C for 30 minutes, thereby measuring the ruthenium-containing film. The mass of the solid component in the composition for formation, and the mass of the solid component is divided by the mass of the composition for forming a ruthenium film.

The composition for forming a ruthenium-containing film can be preferably used as a film-forming material in a resist process including a ruthenium film or the like as an intermediate film in a multilayer resist process, and can also be used in a reverse process. Uses other than the film forming material in the resist process such as the formation material of the pattern (reverse pattern).

<The ruthenium-containing film> The ruthenium-containing film obtained by the composition for forming a ruthenium film is excellent in the etch-resistance of the fluorine-based gas, and is excellent in the collapse resistance of the resist pattern, and is formed on the resist pattern. The alkaline developing solution in the step is excellent in resistance and excellent in peeling property due to alkaline hydrogen peroxide water. Therefore, the composition for forming a ruthenium-containing film can be preferably used as a material for forming a ruthenium-containing film which is an intermediate film in a resist process, particularly a multilayer resist process. In addition, in the multilayer resist process, it is particularly preferable to use a multilayer anti-friction in a finer region (ArF, F ₂ , EUV, nanoimprint, etc.) in a finer region than 90 nm (ArF, F ₂ , EUV, immersion exposure, etc.) Pattern formation of the etchant process.

The ruthenium-containing film can be formed by applying the composition for forming a ruthenium-containing film to a surface of another underlayer film such as a substrate or an organic underlayer film, thereby forming a coating film. The film is heat treated to harden it.

Examples of the method of applying the composition for forming a ruthenium-containing film include a spin coating method, a roll coating method, and a dipping method. The lower limit of the temperature for the heat treatment is preferably 50 ° C, more preferably 70 ° C. The upper limit of the temperature is preferably 450 ° C, more preferably 300 ° C. The lower limit of the average thickness of the formed ruthenium-containing film is preferably 10 nm, more preferably 20 nm. As the upper limit of the average thickness, it is preferably 200 nm, more preferably 150 nm.

<Pattern forming method> The pattern forming method includes a step of forming a ruthenium-containing film on the upper side of the substrate by the application of the ruthenium-containing film-forming composition (hereinafter also referred to as "the ruthenium-containing film forming step"); And a step of patterning the ruthenium-containing film (hereinafter also referred to as "film-containing patterning step").

According to the pattern forming method, since the composition for forming a ruthenium-containing film is used, it is possible to form a ruthenium-containing film which is excellent in the etch-removability of the fluorine-based gas and has excellent collapse resistance of the resist pattern, and It is possible to form a ruthenium-containing film which is excellent in resistance to an alkaline developer in the resist pattern forming step and excellent in peeling property due to alkaline hydrogen peroxide water.

The ruthenium-containing film patterning step may further include a step of forming a resist pattern on the upper side of the ruthenium-containing film (hereinafter also referred to as "resist pattern formation step"); and the resist The step of etching the ruthenium-containing film as a mask (hereinafter also referred to as "ruthenium-containing film etching step").

The pattern forming method may also include a step of forming an organic underlayer film on the upper side of the substrate (hereinafter also referred to as "organic underlayer film forming step") as needed in the ruthenium-containing film forming step. Further, the pattern forming method may further include a step of removing the ruthenium-containing film (hereinafter also referred to as "the ruthenium-containing film removal step") after the ruthenium-containing film formation step. The pattern forming method generally includes a step of etching the substrate by using the patterned ruthenium-containing film as a mask after the ruthenium-containing film patterning step (hereinafter also referred to as "substrate etching step"). Hereinafter, each step will be described.

<Organic Lower Film Forming Step> In this step, an organic underlayer film is formed on the upper side of the substrate. In the pattern forming method, an organic underlayer film forming step can be performed as needed.

In the pattern forming method, in the case of performing the organic underlayer film forming step, the ruthenium-containing film forming step is performed after the organic underlayer film forming step, and the ruthenium-containing film forming composition is used in the ruthenium-containing film forming step. A ruthenium-containing film is formed on the organic underlayer film.

Examples of the substrate include an insulating film such as cerium oxide, cerium nitride, cerium oxynitride, or polyoxyalkylene, and a resin substrate. For example, "Black Diamond" by Applied Materials (AMAT), "Silk" by Dow Chemical, and "LKD5109" by JSR Corporation can be used. An interlayer insulating film such as a wafer coated with a low dielectric insulating film formed by the like. As the substrate, a patterned substrate such as a wiring groove (shallow groove) or a plug groove (channel) can be used.

The organic underlayer film is different from the ruthenium-containing film formed of the composition for forming a ruthenium-containing film. The organic underlayer film further compensates for the function of the ruthenium-containing film and/or the resist film in the formation of the resist pattern, or imparts a predetermined function (for example, anti-reflection) in order to obtain a function that the film does not have. A film of properties, coating film flatness, and high etching resistance to a fluorine-based gas.

Examples of the organic underlayer film include an antireflection film and the like. Examples of the composition for forming an antireflection film include "NFC HM8006" by JSR Corporation.

The organic underlayer film can be formed by applying a composition for forming an organic underlayer film by a spin coating method or the like to form a coating film, followed by heating.

<The ruthenium-containing film formation step> In this step, a ruthenium-containing film is formed on the upper side of the substrate by the application of the ruthenium-containing film-forming composition. By this step, a ruthenium-containing film is formed on the substrate directly or via another layer such as an organic underlayer film.

The method of forming the ruthenium-containing film is not particularly limited, and for example, a coating film is formed by applying the composition for forming a ruthenium-containing film onto a substrate or the like by a known method such as a spin coating method, and the coating film is formed. It is formed by hardening and/or heating to harden it.

Examples of the radiation used for the exposure include electromagnetic waves such as visible rays, ultraviolet rays, far ultraviolet rays, X-rays, and gamma rays, particle beams such as electron beams, molecular beams, and ion beams.

The lower limit of the temperature at the time of heating the coating film is preferably 90 ° C, more preferably 150 ° C, and still more preferably 200 ° C. The upper limit of the temperature is preferably 550 ° C, more preferably 450 ° C, and still more preferably 300 ° C. The lower limit of the average thickness of the formed ruthenium-containing film is preferably 1 nm, more preferably 10 nm, and still more preferably 20 nm. The upper limit of the average thickness is preferably 20,000 nm, more preferably 1,000 nm, and still more preferably 100 nm.

<Phase-containing film patterning step> In this step, the ruthenium-containing film is patterned. By this step, the ruthenium-containing film formed in the ruthenium-containing film formation step is patterned. As a method of patterning the ruthenium-containing film, for example, a method including a resist pattern forming step and a ruthenium-containing film etching step may be mentioned.

[Resist Pattern Forming Step] In this step, a resist pattern is formed on the upper side of the ruthenium containing film. By this step, a resist pattern is formed on the upper side of the ruthenium-containing film formed in the ruthenium-containing film formation step. Examples of the method of forming the resist pattern include a conventionally known method such as a method using a resist composition, a method using a nanoimprint lithography method, and the like. The resist pattern is usually formed of an organic material.

As a method of using the resist composition, for example, a method of forming a resist film on the upper side of the ruthenium-containing film by a resist composition (hereinafter, also referred to as a "resist film forming step"); a step of exposing the resist film (hereinafter also referred to as "exposure step"); and a step of developing the exposed resist film (hereinafter Also known as the "development step").

(Resist Film Forming Step) In this step, a resist film is formed on the upper side of the ruthenium-containing film by a resist composition. A resist film is formed on the upper side of the ruthenium containing film by this step.

Examples of the resist composition include a radiation-sensitive resin composition (chemically amplified resist composition) containing a polymer having an acid-dissociable group and a radiation-sensitive acid generator, and an alkali-soluble resin and A positive resist composition of a quinone diazide-based sensitizer, a negative resist composition containing an alkali-soluble resin and a crosslinking agent, and the like. Among these, a radiation sensitive resin composition is preferred. In the case of using a radiation sensitive resin composition, a positive pattern can be formed by development with an alkaline developer, and a negative pattern can be formed by development with an organic solvent developer. When forming a resist pattern, a double patterning method, a double exposure method, or the like as a method of forming a fine pattern may be suitably used.

The polymer contained in the radiation sensitive resin composition may have, for example, a structural unit including a lactone structure, a cyclic carbonate structure, and/or a sultone structure, in addition to a structural unit containing an acid dissociable group, and an alcoholic property. A structural unit of a hydroxyl group, a structural unit containing a phenolic hydroxyl group, a structural unit containing a fluorine atom, and the like. When the polymer has a structural unit containing a phenolic hydroxyl group and/or a structural unit containing a fluorine atom, sensitivity when using extreme ultraviolet rays (EUV), an electron beam, or the like as radiation during exposure can be improved.

The lower limit of the solid content concentration of the resist composition is preferably 0.1% by mass, preferably 1% by mass. The upper limit of the solid content concentration is preferably 50% by mass, and more preferably 30% by mass. As the resist composition, a resist composition which is filtered by a filter having a pore size of about 0.2 μm can be preferably used. In the pattern forming method, a resist composition of a commercially available product can be directly used as a resist composition.

As a method of forming the resist film, for example, a method of applying a resist composition to a ruthenium-containing film or the like can be mentioned. The coating method of the resist composition is, for example, a conventional method such as a spin coating method. When the resist composition is applied, the amount of the applied resist composition is adjusted such that the obtained resist film has a predetermined film thickness.

Regarding the resist film, the coating film of the resist composition can be pre-baked, whereby the solvent in the coating film is volatilized to form a resist film. The prebaking temperature is appropriately adjusted depending on the type of the resist composition to be used and the like, and the lower limit of the prebaking temperature is preferably 30 ° C, more preferably 50 ° C. The upper limit of the temperature is preferably 200 ° C, more preferably 150 ° C.

(Exposure Step) In this step, the resist film is exposed. The exposure is performed, for example, by selectively irradiating radiation through a reticle.

The radiation used for exposure is a particle beam such as an electromagnetic wave such as a visible ray, an ultraviolet ray, a far ultraviolet ray, an X ray or a gamma ray, an electron beam, a molecular beam, or an ion beam, depending on the type of the acid generator used in the resist composition. Suitable choices, among them, far ultraviolet and electron beams, more preferably KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F ₂ excimer laser light (wavelength 157 nm) ), Kr ₂ excimer laser light (wavelength 147 nm), ArKr excimer laser light (wavelength 134 nm), EUV (wavelength 13 nm, etc.) and electron beam, and thus ArF excimer laser light, EUV and electron beam. Further, the method of exposure is not particularly limited, and it can be carried out according to a method previously performed in pattern formation.

(Developing Step) In this step, the exposed resist film is developed. Thereby, a resist pattern is formed.

The development may be an alkali development or an organic solvent development.

Examples of the alkaline developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, and di-n-propyl. Amine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-di An aqueous alkaline solution obtained by dissolving at least one of a basic compound such as azabicyclo[5.4.0]-7-undecene or 1,5-diazabicyclo[4.3.0]-5-decene. Further, the alkaline aqueous solution may be an alkaline aqueous solution in which a water-soluble organic solvent such as an alcohol such as methanol or ethanol or a surfactant is added in an appropriate amount.

The organic solvent developing solution may, for example, be a solution containing an organic solvent such as a ketone solvent, an alcohol solvent, a guanamine solvent, an ether solvent or an ester solvent as a main component. Examples of the solvent include the same solvent as each of the solvents exemplified as the solvent (B). These solvents may be used singly or in combination of two or more.

After development by a developing solution, it is preferable to carry out washing and drying, whereby a predetermined resist pattern corresponding to the mask can be formed.

[Antimony Film Etching Step] In this step, the resist pattern is used as a mask, and the germanium containing film is etched. More specifically, the patterned ruthenium-containing film is obtained by etching the resist pattern formed in the resist pattern forming step one or more times as a mask.

The etching may be dry etching or wet etching, but is preferably dry etching.

Dry etching can be performed, for example, using a known dry etching apparatus. The etching gas used in the dry etching can be suitably selected by the element composition of the ruthenium-containing film to be etched, and, for example, fluorine compounds such as CHF ₃ , CF ₄ , C ₂ F ₆ , C ₃ F ₈ , and SF ₆ can be used. a gas; a chlorine-based gas such as Cl ₂ or BCl ₃ ; an oxygen-based gas such as O ₂ , O ₃ or H ₂ O; H ₂ , NH ₃ , CO, CO ₂ , CH ₄ , C ₂ H ₂ , C ₂ H ₄ , Reducing gases such as C ₂ H ₆ , C ₃ H ₄ , C ₃ H ₆ , C ₃ H ₈ , HF, HI, HBr, HCl, NO, NH ₃ , BCl ₃ ; inert gases such as He, N ₂ , Ar, etc. . These gases can also be used in combination. In the dry etching of the ruthenium-containing film, a fluorine-based gas is usually used, and a gas in which an oxygen-based gas and an inert gas are mixed is preferably used.

<Substrate Etching Step> In this step, the patterned germanium-containing film is used as a mask and the substrate is etched. More specifically, one or more etchings are performed to obtain a patterned substrate, wherein the etching is performed as a mask with a pattern formed on the ruthenium-containing film obtained in the ruthenium-containing film etching step.

In the case where an organic underlayer film is formed on the substrate, the ruthenium-containing film pattern is used as a mask and the organic underlayer film is etched, thereby forming a pattern of the organic underlayer film, and then the organic underlayer film pattern is used as a mask and The substrate is etched to form a pattern on the substrate.

The etching may be dry etching or wet etching, but is preferably dry etching.

The dry etching in forming a pattern on the organic underlayer film can be carried out using a known dry etching apparatus. The etching gas used in the dry etching can be suitably selected by an elemental composition of the gas-containing tantalum film and the organic underlayer film to be etched, and examples thereof include CHF ₃ , CF ₄ , C ₂ F ₆ , and C ₃ F ₈ . a fluorine-based gas such as SF ₆ ; a chlorine-based gas such as Cl ₂ or BCl ₃ ; an oxygen-based gas such as O ₂ , O ₃ or H ₂ O; H ₂ , NH ₃ , CO, CO ₂ , CH ₄ or C ₂ H ₂ , Reducing gases such as C ₂ H ₄ , C ₂ H ₆ , C ₃ H ₄ , C ₃ H ₆ , C ₃ H ₈ , HF, HI, HBr, HCl, NO, NH ₃ , BCl ₃ ; He, N ₂ , An inert gas such as Ar may be used in combination. An oxygen-based gas is usually used for dry etching of an organic underlayer film in which a pattern containing a ruthenium film is used as a mask.

The dry etching in the case where the organic underlayer film pattern is patterned as a mask on a substrate can be performed using a known dry etching apparatus. The etching gas used for the dry etching can be appropriately selected by the elemental composition of the organic underlayer film and the substrate to be etched, and the like, for example, the same as the etching gas used for the dry etching of the organic underlayer film. Etching gas, etc. Etching can also be performed by multiple different etching gases. Further, in the case where the ruthenium-containing film remains on the substrate or the resist underlayer pattern after the substrate pattern forming step, the ruthenium-containing film can be removed by performing the ruthenium-containing film removal step to be described later.

<The film containing ruthenium removal step> In this step, the ruthenium-containing film is removed after the ruthenium-containing film formation step. When this step is performed after the substrate etching step, the ruthenium containing film remaining on the upper side of the substrate is removed. Further, this step may be performed on the ruthenium-containing film which has been patterned or unpatterned before the substrate etching step. That is, for example, in the case where a defect occurs in the formation of the ruthenium-containing film, or in the case where the patterned ruthenium-containing film before the substrate etching step is defective, by performing this step, the substrate can be discarded. The self-containing ruthenium film forming step is repeated again.

Examples of the method for removing the ruthenium-containing film include a method of dry etching the ruthenium-containing film, a method of bringing a liquid such as an alkaline solution or an acidic liquid into contact with the ruthenium-containing film, and the like. As the liquid, an alkaline liquid is preferred.

The dry etching can be performed using a well-known dry etching apparatus. Further, as the source gas in the dry etching, for example, a fluorine-based gas such as CHF ₃ , CF ₄ , C ₂ F ₆ , C ₃ F ₈ or SF ₆ or a chlorine-based gas such as Cl ₂ or BCl ₃ can be used. Gas can also be mixed and used.

Examples of the alkaline liquid include alkaline hydrogen peroxide water and the like. More specifically, a mixed aqueous solution of ammonia and hydrogen peroxide (25% by mass aqueous ammonia solution/30% by mass aqueous hydrogen peroxide solution/water=1/2/40 (mass ratio) mixed aqueous solution (SC1)) is preferable. In the case of using alkaline hydrogen peroxide water, the wet-peeling method is not particularly limited as long as it is a method in which a ruthenium-containing film and alkaline hydrogen peroxide water can be contacted under heating for a certain period of time, for example, for example. A method of immersing a substrate having a ruthenium-containing film in heated alkaline hydrogen peroxide water, a method of blowing alkaline hydrogen peroxide water in a heating environment, and applying a heated alkaline peroxidation Hydrogen water method, etc. The substrate may be washed with water and dried after each of the methods.

The lower limit of the temperature at which the ruthenium-containing film removal step is carried out using alkaline hydrogen peroxide water is preferably 40 ° C, more preferably 50 ° C. The upper limit of the temperature is preferably 90 ° C, more preferably 80 ° C.

The lower limit of the immersion time in the immersion method is preferably 0.2 minutes, more preferably 0.5 minutes. The upper limit of the immersion time is preferably 30 minutes, more preferably 20 minutes, and still more preferably 10 minutes, and particularly preferably 5 minutes, from the viewpoint of suppressing the influence on the substrate. [Examples]

Hereinafter, examples will be described. Further, the examples shown below show an example of a representative embodiment of the present invention, and the scope of the present invention is not construed as narrowly.

The measurement of the solid content concentration in the solution of [A] polyoxane in the present example and the measurement of the weight average molecular weight (Mw) of [A] polyoxyalkylene were carried out by the following methods.

[[A] Solid Content Concentration of Solution of Polyoxane] A solution of 0.5 g of [A] polyoxane was calcined at 250 ° C for 30 minutes, thereby measuring the mass of the solid component in 0.5 g of the solution. The solid content concentration (% by mass) of the solution of [A] polyoxane was calculated.

[Weight average molecular weight (Mw)] GPC column (2 pieces of "G2000HXL" from Tosoh, 1 "G3000HXL", and 1 "G4000HXL") were used, and the flow rate was 1.0 mL/min, and the solvent was dissolved: Tetrahydrofuran, column temperature: 40 ° C under analytical conditions, determined by gel permeation chromatography (detector: differential refractometer) using monodisperse polystyrene as a standard.

[Average Thickness of Film] The average thickness of the film was measured using a spectroscopic ellipsometer ("M2000D" by J.A. WOOLLAM).

<Synthesis of [A] Polyoxane> The monomer for synthesizing [A] polyoxane is shown below. In the following synthesis examples, the mass parts are values when the total mass of the monomers to be used is 100 parts by mass, unless otherwise specified.

[Chemistry 13]

[Chemistry 14]

[Synthesis Example 1] (Synthesis of Polyoxane (A-1)) The compound represented by the formula (M-1), the compound represented by the formula (M-A1), and the compound in the reaction container The compound represented by the formula (M-A2) was dissolved in 62 parts by mass of propylene glycol monoethyl ether so that the molar ratio became 10/75/15 (mol%) to prepare a monomer solution. While the inside of the reaction vessel was stirred at 60 ° C, 40 parts by mass of a 9.1% by mass aqueous solution of oxalic acid was added dropwise over 20 minutes. The start of the dropwise addition was set as the start time of the reaction, and the reaction was carried out for 4 hours. After completion of the reaction, the inside of the reaction vessel was cooled to 30 ° C or lower. After 52 parts by mass of propylene glycol monoethyl ether was added to the cooled reaction solution, the alcohol formed by the reaction and the remaining propylene glycol monoethyl ether were removed using an evaporator to obtain propylene glycol of polyoxyalkylene (A-1). A solution of diethyl ether. The Mw of the polyoxyalkylene (A-1) was 1,800. The solid content concentration of the propylene glycol monoethyl ether solution of the polyoxyalkylene (A-1) was 10.7% by mass.

[Synthesis Example 2 to Synthesis Example 22] (polyoxane (A-2) to polyoxyalkylene (A-20) and polyoxyalkylene (a-1) and polyoxyalkylene (a-2) Synthesis) Polyoxane (A-2) to polyoxane (A-20) and polyfluorene were obtained in the same manner as in Synthesis Example 1 except that each of the types and amounts of the monomers shown in Table 1 below were used. A solution of oxyalkylene (a-1) and polydecane (a-2) in propylene glycol monoethyl ether. Table 1 shows the Mw of the [A] polyoxane in the obtained solution of the polyoxoxane and the solid content concentration (% by mass).

[Table 1]

<Preparation of a composition for forming a ruthenium film> A component other than the [A] polysiloxane which is used for preparing a composition for forming a ruthenium film is shown below.

[[B] solvent] B-1: propylene glycol monomethyl ether acetate B-2: propylene glycol monoethyl ether

[Example 1] 2.2 parts by mass of (A-1) as [A] polyoxyalkylene (solid component), (B-1) 10 parts by mass of [B] solvent, and (B-2) 90 The mass fraction (also including the solvent (B-2) contained in the solution of [A] polyoxane) was mixed, and the obtained solution was filtered using a filter having a pore size of 0.2 μm to prepare a composition for forming a ruthenium-containing film. (J-1).

[Example 2 to Example 20, Comparative Example 1 and Comparative Example 2] A composition for forming a ruthenium-containing film was prepared in the same manner as in Example 1 except that each component of the type and the amount of the formulation shown in Table 2 below was used. J-2) to a composition for forming a ruthenium-containing film (J-20), a composition for forming a ruthenium-containing film (j-1), and a composition for forming a ruthenium-containing film (j-2).

<Formation of ruthenium-containing film> The prepared ruthenium-containing film was formed by a spin coating method using a spin coater ("CLEAN TRACK ACT12" by Tokyo Electron Co., Ltd.) The composition is applied to a tantalum wafer (substrate). The obtained coating film was heated by a hot plate at 220 ° C for 60 seconds, and then cooled at 23 ° C for 60 seconds, thereby obtaining the formations shown in Examples 1 to 20 of Table 2, and Comparative Example 1 and Comparative Example 2. A ruthenium-containing substrate having an average thickness of 35 nm.

<Evaluation> The following items of the prepared ruthenium-containing film-forming composition and the formed ruthenium-containing film were evaluated by the following methods. The evaluation results are shown together in Table 2 below. The "-" in Table 2 indicates that the corresponding evaluation is not performed.

[Resistance to Alkaline Developer] The substrate on which the ruthenium film was formed was immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) (20 ° C to 25 ° C) for 60 seconds, and washed with water. The average thickness of the film before and after the immersion was measured. When the average thickness before immersion was T ₀ and the average thickness after immersion was T ₁ , the film thickness change rate (%) by immersion in the TMAH aqueous solution was determined by the following formula. Film thickness change rate (%) = │ T _{1 -} T ₀ │ × 100 / T ₀ Regarding the resistance to the alkaline developer, the case where the film thickness change rate is less than 1% is evaluated as "A" (good), and The case of 1% or more was evaluated as "B" (bad).

[Removability by Alkaline Hydrogen Peroxide Water] The substrate containing the ruthenium-containing film is formed in alkaline hydrogen peroxide water (25% by mass aqueous ammonia solution/30% by mass aqueous hydrogen peroxide solution/water = 1/2) The mixture was immersed in a /40 (mass ratio) mixed solution (SC1) at 60 ° C to 65 ° C for 5 minutes, and washed with water. The average thickness of the film before and after the immersion was measured. When the average thickness before immersion is S ₀ and the average thickness after immersion is S ₁ , the film thickness change rate (%) due to immersion in SC1 is obtained by the following formula. Film thickness change rate (%) = (S _{0 -} S ₁ ) × 100 / S ₀ Regarding the peeling property by alkaline hydrogen peroxide water, the case where the film thickness change rate is 99% or more is evaluated as "A" ( Good), the case of less than 99% is evaluated as "B" (bad).

[Sacking inhibition property (1)] (slack suppression property of resist pattern in ArF exposure) The composition for forming an organic underlayer film by spin coating using the spin coater (Jie Shiya ( JSR) "NFC HM8006" was applied to a 12-inch wafer and heat-treated at 250 ° C for 60 seconds to form an organic underlayer film having an average thickness of 100 nm. The obtained composition for forming a ruthenium-containing film was applied onto the organic underlayer film by a spin coating method using the spin coater, and subjected to heat treatment at 220 ° C for 60 seconds, at 23 ° C. It was cooled for 60 seconds, thereby forming a ruthenium-containing film having an average thickness of 35 nm. Then, the radiation-sensitive resin composition ("ARF AR2772JN" of JSR Corporation) was applied onto the ruthenium-containing film by the spin coater, and after heat treatment at 90 ° C for 60 seconds, The film was cooled at 23 ° C for 30 seconds, thereby forming a resist film having an average thickness of 100 nm. Then, an ArF immersion exposure apparatus ("S610C" of Nikon Corporation) was used to perform a mask size mask for forming a 40 nm line/80 nm pitch under the optical conditions of NA: 1.30 and Dipole. exposure. After heating on a hot plate of "Lithius Pro-i" at 100 ° C for 60 seconds, and cooling at 23 ° C for 30 seconds, a 2.38 mass % TMAH aqueous solution was used as a developing solution for 30 seconds. Wash with water. The substrate for evaluation was formed by spin drying at 2,000 rpm for 15 seconds, thereby obtaining a resist pattern having a pitch of 40 nm line/80 nm. A scanning electron microscope ("CG-4000" of Hitachi High-technologies Co., Ltd.) was used for the measurement and observation of the resist pattern of the evaluation substrate. In the formation of the resist pattern, the exposure amount is increased stepwise and exposure is sequentially performed, and the line width corresponding to the maximum exposure amount in which the collapse of the resist pattern is not confirmed is defined as the minimum pre-collapse size ( Nm) is used as an indicator of the collapse inhibition property of the resist pattern. Regarding the collapse inhibition property (1), the case where the minimum collapse size is 32 nm or less is evaluated as "A" (good), and the case where the value exceeds 32 nm and is 38 nm or less is evaluated as "B" (slightly good). The case of exceeding 38 nm was evaluated as "C" (bad).

[Scatter suppression (2)] (slack suppression of resist pattern in electron beam exposure) Antireflection film forming material by spin coating using the spin coater (JSR) The company's "HM8006" was applied to an 8-inch wafer and heated at 250 ° C for 60 seconds to form an anti-reflection film having an average thickness of 100 nm. The ruthenium-containing film-forming composition was applied onto the anti-reflection film, heated at 220 ° C for 60 seconds, and then cooled at 23 ° C for 30 seconds, thereby forming a ruthenium-containing film having an average thickness of 35 nm. Then, the radiation-sensitive resin composition described later was applied onto a ruthenium-containing film, and heat-treated at 130 ° C for 60 seconds, and then cooled at 23 ° C for 30 seconds to form a resist film having an average thickness of 50 nm. The radiation sensitive resin composition is obtained by having a structural unit derived from 4-hydroxystyrene (1), a structural unit derived from styrene (2), and derived from 4-third 100 parts by mass of the structural unit (3) of oxystyrene (the content ratio of each structural unit is (1) / (2) / (3) = 65 / 5 / 30 (mol%)) 2.5 parts by mass of triphenylsulfonium salicylate of a radioactive acid generator, 1,500 parts by mass of ethyl lactate as a solvent, and 700 parts by mass of propylene glycol monomethyl ether acetate, and a filter having a pore size of 0.2 μm was used. The solution was filtered. Then, the resist film was irradiated with an electron beam using an electron beam drawing device ("HL800D" of Hitachi, Ltd., output: 50 KeV, current density: 5.0 amp/cm ² ). After the irradiation of the electron beam, the substrate was heated at 110 ° C for 60 seconds, and then cooled at 23 ° C for 60 seconds, and then developed using a 2.38 mass % TMAH aqueous solution (20 ° C to 25 ° C) by a liquid coating method. The substrate for evaluation in which the resist pattern was formed was obtained by washing with water and drying. When the resist pattern is formed, an exposure amount of a 1:1 line and space formed at a line width of 150 nm is set as an optimum exposure amount. A scanning electron microscope ("CG-4000" of Hitachi High-technologies Co., Ltd.) was used for the measurement and observation of the resist pattern of the evaluation substrate. Regarding the collapse inhibition property (2), in the optimum exposure amount, the case where the pattern collapse was not confirmed was evaluated as "A" (good), and the case where the pattern collapse was confirmed was evaluated as "B" (bad) ).

[Etase removal by fluorine-based gas] Using an etching apparatus (TACTRAS of Tokyo Electron Co., Ltd.), CF ₄ = 200 sccm, PRESS. = 75 mT, HF RF = Under the conditions of 250 W, LF RF=0 W, DCS=-150 V, RDC=50%, and 5 sec, the substrate on which the obtained ruthenium-containing film is formed is etched, and is calculated according to the average film thickness before and after the treatment. The etching rate (nm/min) was measured, and the etching removal property by the fluorine-based gas was evaluated. Regarding the etching removal property by the fluorine-based gas, the case where the etching rate is 60 (nm/min) or more is evaluated as "A" (good), and 55 (nm/min) or more and less than 60 (nm/min). The case was evaluated as "B" (slightly good), and the case of less than 55 (nm/min) was evaluated as "C" (bad).

[Storage Stability] The composition for forming a ruthenium-containing film prepared as described above was stored at -15 ° C and 40 ° C for 7 days, and then the weight average molecular weight (Mw) of the [A] polyoxane in the composition was measured. . The storage stability was evaluated as "A" (good) when the difference between the Mw stored at -15 ° C and the Mw stored at 40 ° C was less than 100, and the case where 100 or more and less than 1,000 was evaluated as "B" (slightly good), the case of 1,000 or more was evaluated as "C" (bad).

[Table 2]

According to the results of Table 2, the composition for forming a ruthenium-containing film of the examples is excellent in storage stability, excellent in resistance to an alkaline developer, and excellent in peeling property due to alkaline hydrogen peroxide water, and is caused by a fluorine-based gas. A ruthenium-containing film which is excellent in etching removability and excellent in suppressing collapse resistance of a resist pattern. In general, it is known that the electron beam exposure shows the same tendency as in the case of EUV exposure. Therefore, according to the composition for forming a ruthenium film according to the embodiment, it is presumed that even in the case of EUV exposure, the resist pattern is The collapse inhibition is also excellent. [Industrial availability]

According to the ruthenium-containing film-forming composition and the pattern forming method of the present invention, it is possible to form a ruthenium-containing film which is excellent in the etch-eliminability by the fluorine-based gas and has excellent collapse resistance of the resist pattern, and can form a confrontation. The ruthenium-containing film which is excellent in the resistance of the alkaline developing solution in the etchant pattern forming step and excellent in the peeling property by the alkaline hydrogen peroxide water. Further, the composition for forming a ruthenium-containing film of the present invention is also excellent in storage stability. The ruthenium-containing film of the present invention maintains the etching removeability by the fluorine-based gas, and is excellent in resistance to an alkaline developer and excellent in peelability due to alkaline hydrogen peroxide water. The polyoxyalkylene of the present invention can be preferably used as the polyoxymethane component of the composition for forming a ruthenium-containing film. Therefore, these can be preferably used for a multilayer resist process, and can be preferably used for the manufacture of a semiconductor device in which further miniaturization is expected in the future.

no

no

Claims (15)

A composition for forming a ruthenium film, comprising: a polyoxyalkylene having a group represented by the following formula (1); and a solvent; In the formula (1), L is a single bond or an (n+1)-valent organic group having 1 to 20 carbon atoms; and E is a group represented by the following formula (2-1) or (2-2); An integer of 1 to 3; when n is 2 or more, L is an organic group, and a plurality of E are the same or different; * represents a site bonded to a germanium atom in the polyoxyalkylene; In the formula (2-1), R ¹ is a single bond or a divalent organic group having 1 to 20 carbon atoms; Y ¹ is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or at least one hydrogen atom is pulled. An electron-based substituted monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms; wherein, in the formula (2-2), R ² is a monovalent organic group having 1 to 20 carbon atoms; and Y ² is a substituted or unsubstituted carbon A divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which is substituted with an electron withdrawing group of 6 to 20 or less of an aromatic hydrocarbon group. The composition for forming a ruthenium-containing film according to claim 1, wherein the polyoxyalkylene has a first structural unit represented by the following formula (3); In the formula (3), Z is a group represented by the formula (1); R ³ is a monovalent organic group having 1 to 20 carbon atoms which does not contain -SO ₂ O-, a hydrogen atom or a hydroxyl group; m is 0. An integer of ～2; where m is 2, the two R ^{3 are the} same or different. The composition for forming a ruthenium-containing film according to the first or second aspect of the invention, wherein the electron withdrawing group is a halogen atom, a cyano group, a halogenated hydrocarbon group having 1 to 10 carbon atoms, and a carbon number of 1 to 10. a group having -O-, a group having -SO- having 1 to 10 carbon atoms, a group having -SO ₂ - having 1 to 10 carbon atoms, a group having -CO- having 1 to 10 carbon atoms or a carbon number 1 to 10 groups having -COO-. The composition for forming a ruthenium-containing film according to the first aspect, the second aspect, or the third aspect, wherein Y ¹ in the formula (2-1) is a substituted or unsubstituted aryl group or a group represented by the following formula (4-1), wherein Y ² in the formula (2-2) is a substituted or unsubstituted arene diyl group; In the formula (4-1), R ⁴ to R ⁸ are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 18 carbon atoms or a monovalent electron-donating group; p is 0 or 1; wherein, p is 0 In the case, at least one of R ⁶ to R ⁸ is an electron withdrawing group; and when p is 1, at least one of R ⁴ to R ⁸ is an electron withdrawing group. The composition for forming a ruthenium-containing film according to the second aspect of the invention, wherein the polysiloxane has a second structural unit represented by the following formula (5), . The composition for forming a ruthenium-containing film according to any one of claims 2 to 5, wherein the polyoxy siloxane further has a third structural unit represented by the following formula (6); In the formula (6), R ^A is a monovalent organic group having 1 to 20 carbon atoms which does not contain -SO ₂ O-; a is 1 or 2; and when a is 2, the two R ^{A are the} same or different. The composition for forming a ruthenium-containing film according to any one of claims 2 to 6, wherein the content ratio of the first structural unit to all structural units constituting the polyoxyalkylene is 0.1 mol% or more and 50 mol% or less. The composition for forming a ruthenium-containing film according to any one of claims 1 to 7, which is used for a resist process. A ruthenium-containing film, which is formed by the composition for forming a ruthenium-containing film according to any one of the first to eighth aspects of the invention. A pattern forming method, comprising: a step of forming a ruthenium-containing film on an upper side of a substrate by coating a composition for forming a ruthenium-containing film according to any one of claims 1 to 8; And a step of patterning the ruthenium containing film. The pattern forming method according to claim 10, further comprising the step of removing the ruthenium-containing film after the ruthenium-containing film forming step. The pattern forming method according to claim 11, wherein the step of removing the ruthenium-containing film is to remove an alkaline liquid from the ruthenium-containing film to remove the ruthenium-containing film. The pattern forming method according to claim 10, wherein the ruthenium-containing film patterning step comprises: forming a resist pattern on an upper side of the ruthenium-containing film; The step of etching the ruthenium-containing film by using the resist pattern as a mask. The pattern forming method according to any one of claims 10 to 13, further comprising the step of forming an organic underlayer film on the upper side of the substrate before the ruthenium-containing film forming step. A polyoxyalkylene having a group represented by the following formula (1); In the formula (1), L is a single bond or an (n+1)-valent organic group having 1 to 20 carbon atoms; and E is a group represented by the following formula (2-1) or (2-2); An integer of 1 to 3; when n is 2 or more, L is an organic group, and a plurality of E are the same or different; * represents a site bonded to a germanium atom in the polyoxyalkylene; In the formula (2-1), R ¹ is a single bond or a divalent organic group having 1 to 20 carbon atoms; Y ¹ is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or at least one hydrogen atom is pulled. An electron-based substituted monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms; wherein, in the formula (2-2), R ² is a monovalent organic group having 1 to 20 carbon atoms; and Y ² is a substituted or unsubstituted carbon A divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which is substituted with an electron withdrawing group of 6 to 20 or less of an aromatic hydrocarbon group.