TW201546183A - Composition for silicon-containing film formation, pattern-forming method, and polysiloxane compound - Google Patents

Abstract

A composition for silicon-containing film formation includes a polysiloxane compound and a solvent. The polysiloxane compound includes a structure represented by formula (Q2), a structure represented by formula (Q3) and a structure represented by formula (Q4). A value of q calculated according to formula (I) is no greater than 0.25, wherein q1 to q4 represent integrated intensities of 29Si-NMR signals due to the silicon atoms in the structures represented by the formulae (Q1) to (Q4), respectively. A weight average molecular weight of the polysiloxane compound is no greater than 4,000. q=(q1+q2)/(q1+q2+q3+q4) formula (I).

Description

Composition for forming ruthenium film, pattern forming method, and polyoxyalkylene compound

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

In recent years, with the miniaturization of semiconductor elements and the like, it has been required to form a finer photoresist pattern. In response to this demand, various multilayer photoresist processes using photoresist underlayer films have been developed. As such a multilayer photoresist process, the following are mentioned, for example. First, a photoresist underlayer film is formed on the substrate to be processed by using a photoresist underlayer film forming composition containing polyoxyalkylene. Next, a photoresist film is formed on the photoresist underlayer film using a photoresist composition. The photoresist film and the photoresist underlayer film are organic films different in etching selectivity. Thereafter, the photoresist film is exposed, and a photoresist pattern is obtained by developing with a developing liquid. Subsequently, by transferring the photoresist pattern to the photoresist underlayer film and the substrate to be processed by dry etching, a substrate to which the desired pattern is applied can be obtained.

However, when the composition for forming a lower layer film of the above-mentioned photoresist is used, it is easy to cause a photo-resist pattern collapse formed on the underlayer film of the photoresist, that is, a so-called pattern collapse. Also, the shape of the light resistance easily becomes the bottom drag Tail shape. The generation of the above-mentioned pattern collapse is particularly remarkable in the negative-type development using an organic solvent, and an additive such as an acid generator is used in order to reduce the collapse of the pattern (refer to Japanese Laid-Open Patent Publication No. 2010-85912 and JP-A-2008). -39811 bulletin). In addition, in order to reduce the bottom tail of the photoresist, a composition containing a naphthenic compound having a mass average molecular weight within a specific range is used (see JP-A-2007-272168). However, these techniques do not adequately coexist with the reduction of pattern collapse and the reduction of the bottom tail of the photoresist.

Moreover, the composition for forming a photoresist film for the lower layer of the prior art has a solvent resistance which is low in the step before the coating film is cured to form a photoresist underlayer film, and the film thickness before curing is likely to change. Further, in the storage of the composition for forming a film under the photoresist, the molecular weight is likely to change and the storage stability is insufficient.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-85912

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-39811

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-272168

The present invention has been made in view of the above circumstances, and its purpose The invention provides a ruthenium having high storage stability in a multilayer photoresist process, particularly in the case of organic solvent development, excellent pattern collapse resistance, reduced bottom tailing of the pattern, and excellent solvent resistance before hardening. A film forming composition, a pattern forming method, and a polyoxyalkylene compound.

In order to solve the above problems, the present invention provides a composition for forming a ruthenium-containing film, which comprises a polysiloxane compound and a solvent; and the polyoxy siloxane compound is represented by the following formulas (Q1) to (Q4) The structure shown (hereinafter also referred to as "structure (Q1) to (Q4)" or "specific alkane structure") has a structure represented by (Q2), a structure represented by (Q3), and In the structure indicated by Q4), among the signals obtained by ²⁹ Si-NMR, the integral value of the signal supplied from each of the germanium atoms in the structures represented by the following formulas (Q1) to (Q4) is set to In the case of q1 to q4, the value of q calculated by the following formula (I) is 0.25 or less, and the weight average molecular weight is 4,000 or less; q = (q1 + q2) / (q1 + q2 + q3 + q4) (I)

(In the formulae (Q1) to (Q4), each of R is independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. However, R is a group which does not contain a ruthenium atom. * indicates a bond. In the part of the atom. )

Another invention to solve the above problems is a pattern forming method comprising the steps of forming a ruthenium-containing film on one surface of a substrate to be processed using the composition for forming a ruthenium-containing film; using a photoresist a composition, a step of forming a photoresist film on the ruthenium-containing film; a step of exposing the photoresist film by light irradiation through a photomask; and a step of developing an exposed photoresist film to form a photoresist pattern; And the step of dry etching the ruthenium containing film and the substrate to be processed by using the photoresist pattern as a mask.

Furthermore, another invention to solve the above problems is a polyoxyalkylene compound characterized by having the structure represented by (Q2) among the structures represented by the above formulas (Q1) to (Q4). Among the signals represented by (Q3) and the structure represented by (Q4), among the signals obtained by ²⁹ Si-NMR, the respective ytterbium atoms in the structures represented by the above formulas (Q1) to (Q4) When the integrated value of the supplied signal is q1 to q4, the value of q calculated by the above formula (I) is 0.25 or less, and the weight average molecular weight is 4,000 or less; here, " ²⁹ Si-NMR" represents Nuclear magnetic resonance spectroscopy of helium atoms. "Organic group" means a group containing at least one carbon atom.

The composition for forming a ruthenium-containing film of the present invention, the pattern forming method, and the polyoxyalkylene compound have high storage stability, and at the same time, can suppress pattern collapse in a multilayer photoresist process, particularly in organic solvent development. The bottom of the photoresist is tailed and the solvent resistance before hardening is excellent. Therefore, this is the same In the formation of a pattern in semiconductor device manufacturing or the like which is expected to be miniaturized in the future, it is possible to use it.

<Composition for forming a ruthenium film>

The composition for forming a ruthenium-containing film contains a polyoxy siloxane compound (A) and a solvent. Since the composition for forming a ruthenium-containing film contains the polysiloxane compound (A), it is possible to form a film excellent in adhesion to the photoresist film. As a result, the pattern collapse of the formed pattern and the bottom tail of the photoresist can be reduced. Further, the composition for forming a ruthenium-containing film may contain an optional component such as an acid generator, without impairing the effects of the present invention. Hereinafter, each component will be described.

<Polyoxyalkylene compound (A)>

The polyoxyalkylene compound (A) has a structure represented by (Q2), a structure represented by (Q3), and a structure represented by (Q4) in a specific oxane structure. Further, among the signals obtained by ²⁹ Si-NMR, when the integral value of the signal supplied from each of the argon atoms in the specific siloxane structure is q1 to q4, q calculated by the following formula (I) The value is 0.25 or less, and the weight average molecular weight is 4,000 or less.

q=(q1+q2)/(q1+q2+q3+q4) (I)

In the composition for forming a ruthenium-containing film, the polyoxonane compound (A) has the above structure, and the value of q is 0.25 or less, and the weight average molecular weight is 4,000 or less, thereby having high storage stability and capable of It suppresses the collapse of the pattern and the tailing of the bottom of the pattern, and is excellent in solvent resistance before hardening.

The value of q above is usually 0.01 or more. The upper limit of the value of q is 0.25 as described above, preferably 0.2, and preferably 0.15. By making the value of q smaller than the above upper limit, the storage stability is improved, and the pattern collapse and the bottom tail of the pattern can be further suppressed, and the solvent resistance before curing is more excellent.

In the above formulae (Q1) to (Q4), R is a hydrogen atom or an organic group having a monovalent number of carbon atoms of 1 to 20. However, R is a person who does not contain a helium atom. * indicates that the bond is bonded to the atom of the atom. When R is an organic group, R is bonded to an oxygen atom adjacent to the ruthenium atom by a carbon atom. The organic group having a valence of 1 to 20 carbon atoms represented by the above-mentioned R is, for example, the same as the organic group exemplified as X described later. In a specific oxane structure, the binding site indicated by * on the oxygen atom is bonded to other ruthenium atoms in the polyoxyalkylene (A). This other ruthenium atom can also be found in a particular oxane structure. At this time, the adjacent specific oxane structures share the oxygen atoms with each other.

The reason why the above-described effect is achieved by the above-described composition of the composition for forming a ruthenium-containing film is not completely clear, but for example, the following reasons can be presumed. In other words, it is considered that since the content ratio of the structure (Q1) and the structure (Q2) is small, the structure of the polyoxyalkylene compound (A) has high regularity, and the alignment property and density of the polar group are improved. In addition, since the weight average molecular weight of the polyoxyalkylene compound (A) is at most the above upper limit, it is considered that the specific decane structure is more in the composition for forming a ruthenium-containing film containing the polyoxy siloxane compound (A). Evenly distributed, and the above regularity is further improved. With this, All of the decane structure of the polyoxyalkylene compound (A) interacts with a carboxyl group or the like in the photoresist film, and the adhesion between the ruthenium-containing film containing the polysiloxane compound (A) and the photoresist film is improved. As a result, pattern collapse and bottom tailing are suppressed. Further, it is considered that the stability of the composition for forming a ruthenium-containing film is improved due to the uniform distribution of the specific siloxane structure described above, and as a result, the solvent resistance and storage stability of the composition for forming a ruthenium-containing film before curing are obtained. Sexual improvement. Here, the "oxygen alkane structure" means a structure containing -Si-O-.

Further, the lower limit of the value of q' represented by the following formula (II) is preferably 0.2, more preferably 0.25. On the other hand, as the upper limit of the value of q' above, 0.7 is preferred, and 0.6 is preferred. Further, in the following formula (II), q1 to q4 are synonymous with the above formula (I).

q’=(q4)/(q1+q2+q3+q4) (II)

Therefore, by setting the ratio of the structure (Q4) to the sum of the specific oxane structures within the above range, the regularity of the above polyoxy siloxane compound (A) is further improved, and as a result, the pattern collapse and the bottom are further suppressed. Trailing.

Further, in the present specification, the integral value of the signal obtained by ²⁹ Si-NMR is a value measured using, for example, a nuclear magnetic resonance apparatus of Bruker BioSpin.

The lower limit of the ratio of the ruthenium atom in the specific oxane structure to the total ruthenium atom of the polyoxy siloxane compound (A) is preferably 50 mol%, more preferably 60 mol%, and 70 mol%. Ear % is better. By setting the ratio of the ruthenium atoms in the specific oxane structure above the above lower limit, the regularity of the structure of the polyoxy siloxane compound (A) is further improved, and pattern collapse and bottom smearing can be further suppressed.

[Synthesis method of polyoxyalkylene compound]

As a method for synthesizing the polyoxyalkylene compound (A), a method of condensing a compound represented by the following formula (1) (hereinafter also referred to as "compound (I)") using an acid is preferred. By this acid, since Z ⁺ in the compound (I) is substituted by a hydrogen atom, sterolization is caused, and a condensation reaction is caused.

In the above formula (1), X is -O ^- Z ⁺ or a monovalent organic group having 1 to 20 carbon atoms. Z ⁺ is a monovalent cation.

Examples of the organic group having a monovalent number of carbon atoms of 1 to 20 represented by X include a monovalent hydrocarbon group, a carbon-carbon-containing group containing a hetero atom group, and a hydrogen atom of the group. A part or all of a group substituted by a substituent or the like.

Examples of the chain hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; and an alkenyl group such as a vinyl group, a propenyl group or a butenyl group; An alkynyl group such as an ethynyl group, a propynyl group or a butynyl group.

Examples of the alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a decyl group or an adamantyl group; a cyclopropenyl group, a cyclopentenyl group, a cyclohexenyl group, and a lower group; A cycloalkenyl group such as a decyl group.

Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a tolyl group, a fluorenyl group, a naphthyl group or a fluorenyl group; and an aralkyl group such as a benzyl group, a phenethyl group or a naphthylmethyl group.

The above hetero atom-containing group means a group having a hetero atom having two or more valences in the structure. The hetero atom-containing group may have one hetero atom or two or more.

The hetero atom having two or more valences of the hetero atom-containing group is not particularly limited as long as it has a valence of two or more valences, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, a ruthenium atom, and phosphorus. Atom, boron atom, etc.

Examples of the hetero atom-containing group include a group consisting of only a hetero atom such as -SO-, -SO ₂ -, -SO ₂ O-, or -SO ₃ -; -CO-, -COO-, - A combination of a carbon atom and a hetero atom such as COS-, -CONH-, -OCOO-, -OCOS-, -OCONH-, -SCONH-, -SCSNH-, -SCSS-, and the like.

Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, and a cyano group.

Examples of the monovalent cation represented by the above Z ⁺ include an ion of an alkali metal such as lithium, sodium, potassium or rubidium; a phosphonium ion such as an ammonium ion or a cesium ion. Among these, ruthenium ions are preferred, ammonium ions are preferred, and ammonium ions of 4 grades are more preferred.

The above X is preferably an -O ^- Z ⁺ , an alkyl group, an aromatic hydrocarbon group or a hetero atom-containing alicyclic hydrocarbon group, and -O ^- Z ⁺ , a methyl group, a phenyl group, an alkylphenyl group, and a cyclic group. The base of the anhydride structure is preferred, and -O ^- Z ⁺ and phenyl are more preferred.

Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; and organic acids such as acetic acid, oxalic acid, maleic acid, formic acid, trifluoroacetic acid, and trifluoromethanesulfonic acid. Among these, an organic acid is preferred, a carboxylic acid is preferred, and oxalic acid and maleic acid are more preferred.

The amount of the acid to be used is preferably 0.2 mol or less, and preferably 0.00001 mol or more and 0.1 mol or less, from the viewpoint of promoting the condensation reaction, with respect to the compound (1) 1 mol.

The reaction solvent to be used in the above condensation reaction is not particularly limited, and usually the same solvent as used in the preparation of the composition for forming a ruthenium-containing film described later can be used. Among these, methanol, butanol, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate And 3-methoxypropionic acid methyl group is preferred.

The lower limit of the reaction temperature of the above compound (I) with the above acid is preferably 0 °C. On the other hand, the upper limit of the above reaction temperature is preferably 15 ° C, and preferably 10 ° C. Reaction time of the above compound (I) with the above acid The lower limit is preferably 15 and preferably 30. On the other hand, the upper limit of the above reaction time is preferably 24 hours, preferably 12 hours. The condensation reaction can be efficiently carried out by setting the reaction temperature and the reaction time within the above range.

(Synthesis method of compound (I))

The method for synthesizing the compound (I) is not particularly limited, and for example, a method of hydrolyzing and condensing a tetrafunctional hydrolyzable decane compound with a high concentration of a base can be mentioned.

Examples of the above-mentioned tetrafunctional hydrolyzable decane compound include tetramethoxynonane, tetraethoxydecane, tetra-n-propoxydecane, tetra-iso-propoxydecane, and tetra-n-butoxy group. a tetraalkoxynonane such as decane, tetra-sec-butoxydecane or tetra-t-butoxydecane; tetraaryl decane such as tetraphenoxydecane; and the like. Among them, tetraalkoxy decane is preferred, and tetramethoxy decane is more preferred.

Examples of the base include nitrogen-containing compounds such as ammonia, a primary amine, a secondary amine, a tertiary amine, and pyridine; a basic ion exchange resin; a hydroxide such as sodium hydroxide; and potassium carbonate. a carbonate; a carboxylate such as sodium acetate; an alkoxide such as an azide oxide, a titanium alkoxide or an alkane oxide. Among them, a 4-stage ammonium salt is preferred, and tetrahydroammonium hydroxide is preferred.

The amount of the base to be used is preferably 2 mol or less, and 0.8 mol or more and 1.2 mol or less, based on the above-mentioned tetrafunctional hydrolyzable decane compound 1 mol, from the viewpoint of promoting the hydrolysis condensation reaction. Preferably.

The water used for the above hydrolysis and condensation is preferably water which is purified by a method such as reverse osmosis membrane treatment, ion exchange treatment, distillation or the like. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved. The lower limit of the amount of water used per 1 mole of the hydrolyzable group relative to the decane compound is preferably 0.1 mol, more preferably 0.3 mol, more preferably 0.5 mol. On the other hand, the upper limit of the amount of water used is preferably 3 moles, preferably 2 moles, more preferably 1.5 moles. When the amount of water used is within the above range, the reaction rate of hydrolysis condensation can be optimized.

The reaction solvent to be used for the above hydrolysis and condensation is not particularly limited, and usually the same solvent as that used for the preparation of the composition for forming a ruthenium-containing film described later can be used. Among these, methanol, butanol, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate And 3-methoxypropionic acid methyl group is preferred.

The reaction temperature and reaction time of the above hydrolysis condensation are suitably set. The lower limit of the reaction temperature is preferably 40 ° C, and preferably 50 ° C. On the other hand, the upper limit of the above reaction temperature is preferably 200 ° C, and preferably 150 ° C. The lower limit of the reaction time is preferably 30, preferably 1 hour. On the other hand, the upper limit of the above reaction time is preferably 24 hours, preferably 12 hours. By allowing the reaction temperature and the reaction time to be within the above range, the hydrolysis condensation reaction can be carried out most efficiently. In this hydrolysis condensation, the tetrafunctional hydrolyzable decane compound, water and catalyst can be used once. The reaction may be carried out in a single step by addition to the reaction system, or may be carried out in multiple stages by adding a tetrafunctional hydrolyzable decane compound, water and a catalyst to the reaction system in several stages. Further, after the hydrolysis condensation reaction, water and the generated alcohol can be removed from the reaction system by evaporation.

Further, a trifunctional hydrolyzable decane compound may be added during the condensation reaction and the hydrolysis condensation. According to this, by adding a trifunctional hydrolyzable decane compound, the optical properties and etching resistance of the ruthenium-containing film containing the polyoxy siloxane compound (A) can be controlled, and as a result, the resolution of the formed photoresist pattern can be obtained. improve.

Examples of the trifunctional hydrolyzable decane compound include an aromatic ring-containing trialkoxy decane, an alkyltrialkoxide decane, an alkenyl trialkoxy decane, an epoxy group-containing decane, and an acid anhydride group-containing group. Decane and so on.

Examples of the above-mentioned aromatic ring-containing trialkoxy decane include phenyltrimethoxydecane, benzyltrimethoxydecane, phenethyltrimethoxydecane, and 4-methylphenyltrimethoxydecane. 4-ethylphenyltrimethoxydecane, 4-methoxyphenyltrimethoxydecane, 4-phenoxyphenyltrimethoxydecane, 4-hydroxyphenyltrimethoxydecane, 4-aminobenzene Trimethoxy decane, 4-dimethylaminophenyl trimethoxy decane, 4-ethyl decyl phenyl trimethoxy decane, 3-methylphenyl trimethoxy decane, 3-ethyl benzene Trimethoxy decane, 3-methoxyphenyl trimethoxy decane, 3-phenoxyphenyl trimethoxy decane, 3-hydroxyphenyl trimethoxy decane, 3-aminophenyl trimethoxy decane , 3-dimethylaminophenyltrimethoxydecane, 3-ethenylaminophenyltrimethoxydecane, 2-methylphenyltrimethoxyindole Alkane, 2-ethylphenyltrimethoxydecane, 2-methoxyphenyltrimethoxydecane, 2-phenoxyphenyltrimethoxydecane, 2-hydroxyphenyltrimethoxydecane, 2-amine Phenyltrimethoxydecane, 2-dimethylaminophenyltrimethoxydecane, 2-ethenylaminophenyltrimethoxydecane, 2,4,6-trimethylphenyltrimethoxy Decane, 4-methylbenzyltrimethoxydecane, 4-ethylbenzyltrimethoxydecane, 4-methoxybenzyltrimethoxydecane, 4-phenoxybenzyltrimethoxydecane, 4- Hydroxybenzyltrimethoxydecane, 4-aminobenzyltrimethoxydecane, 4-dimethylaminobenzyltrimethoxydecane, 4-ethenylaminobenzyltrimethoxydecane, and the like.

Examples of the alkyltrialkoxyoxydecane include methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane, and methyltri-iso-propoxyl. Decane, methyl tri-n-butoxydecane, methyl tri-sec-butoxydecane, methyl tri-t-butoxydecane, methyltriphenyloxydecane, methyltriethoxycarbonyl Decane, methyltrichlorodecane, methyltriisopropenyloxydecane, methyl quinone (dimethylmethoxyoxy)decane, methyl ginseng (methoxyethoxy)decane, methyl ginseng (methyl b) Ketone oxime) decane, methyl ginseng (trimethyl decyloxy) decane, methyl decane, ethyl trimethoxy decane, ethyl triethoxy decane, ethyl tri-n-propoxy decane, Tris-iso-propoxydecane, ethyltri-n-butoxydecane, ethyltris-sec-butoxydecane, ethyltri-t-butoxydecane, ethyltriphenoxydecane , ethyl ginseng (trimethyl decyloxy) decane, ethyl dichloro decane, ethyl triethoxy decane, ethyl trichloro decane, n-propyl trimethoxy decane, n- propyl three Ethoxy decane, n-propyl tri-n-propoxy decane, n-propyl tri-iso-prop Oxydecane, n-propyl tri-n-butoxydecane, n-propyl tris-sec-butoxy fluorene Alkane, n-propyltri-t-butoxydecane, n-propyltriphenoxydecane, n-propyltriethoxydecane, n-propyltrichloromethane, iso-propyltrimethoxy Baseline, iso-propyltriethoxydecane, iso-propyltri-n-propoxydecane, iso-propyltri-iso-propoxydecane, iso-propyltri-n-butoxy Decane, iso-propyltris-sec-butoxydecane, iso-propyltri-t-butoxydecane, iso-propyltriphenoxydecane, n-butyltrimethoxydecane, n-butyl Triethoxy decane, n-butyl tri-n-propoxy decane, n-butyl tri-iso-propoxy decane, n-butyl tri-n-butoxy decane, n-butyl Tris-sec-butoxydecane, n-butyltri-t-butoxydecane, n-butyltriphenoxydecane, n-butyltrichlorodecane, 2-methylpropyltrimethoxydecane , 2-methylpropyltriethoxydecane, 2-methylpropyltri-n-propoxydecane, 2-methylpropyltri-iso-propoxydecane, 2-methylpropyltri -n-butoxydecane, 2-methylpropyltris-sec-butoxydecane, 2-methylpropyltri-t-butoxydecane, 2-methylpropyltriphenoxydecane, 1-methylpropyltrimethoxydecane, 1- Propyltriethoxydecane, 1-methylpropyltri-n-propoxydecane, 1-methylpropyltri-iso-propoxydecane, 1-methylpropyltri-n-butyl Oxydecane, 1-methylpropyltris-sec-butoxydecane, 1-methylpropyltri-t-butoxydecane, 1-methylpropyltriphenoxydecane, t-butyl Trimethoxy decane, t-butyl triethoxy decane, t-butyl tri-n-propoxy decane, t-butyl tri-iso-propoxy decane, t-butyl tri-n-butyl Oxydecane, t-butyltris-sec-butoxydecane, t-butyltri-t-butoxydecane, t-butyltriphenoxydecane, t-butyltrichloromethane, t- Butyl dichlorodecane, and the like.

Examples of the above alkenyl trialkoxy decane include vinyl trimethoxy decane, vinyl triethoxy decane, and vinyl tri- N-propoxydecane, vinyl triisopropoxydecane, vinyl tri-n-butoxydecane, vinyl tri-sec-butoxydecane, vinyl tri-t-butoxydecane, ethylene Triphenyloxydecane, allyltrimethoxydecane, allyltriethoxydecane,allyltri-n-propoxydecane,allyltriisopropoxydecane,allyl III -n-butoxydecane, allyl tri-sec-butoxydecane, allyl tri-t-butoxydecane, allyltriphenoxydecane, and the like.

Examples of the epoxy group-containing decane include propylene oxide-based trimethoxy decane, oxiranyl trimethoxy decane, oxiranylmethyltrimethoxy decane, and 3-epoxypropyl acrylate. Oxypropyltrimethoxydecane, and the like.

Examples of the acid anhydride group-containing decane include 2-[3-(trimethoxyindolyl)propyl]anhydrosuccinic acid, 2-(trimethoxyindolyl)ethyl anhydrous succinic acid, and 3-( Trimethoxyindenyl)propyl anhydrous maleic acid, 2-(trimethoxyindenyl)ethyl anhydrous glutaric acid, and the like.

The trifunctional hydrolyzable decane compound is preferably an aromatic ring-containing trialkoxy decane, an alkyltrialkoxy decane or an acid anhydride group-containing decane, and phenyltrimethoxydecane, benzyltrimethoxydecane, 4-methylphenyltrimethoxydecane, methyltrimethoxydecane, methyltriethoxydecane, and 2-[3-(trimethoxyindolyl)propyl]anhydrosuccinic acid are preferred.

The lower limit of the amount of the trifunctional hydrolyzable decane compound to be added is preferably 1 part by mass, and preferably 3 parts by mass, based on 100 parts by mass of the tetrafunctional hydrolyzable decane compound. On the other hand, the upper limit of the above-mentioned addition amount is preferably 15 parts by mass, and more preferably 12 parts by mass. By making 3 officials When the amount of the hydrolyzable decane compound added is within the above range, the optical properties of the ruthenium-containing film and the like can be more reliably controlled.

In addition, the lower limit of the ratio of the tetrafunctional hydrolyzable decane compound is preferably 50 mol%, and preferably 60 mol%, based on the total amount of the hydrolyzable decane compound used in the synthesis of the polyoxyalkylene compound (A). It is better to use 70 mol%. When the ratio of the tetrafunctional hydrolyzable decane compound is at least the above lower limit, the structure of the polyoxy siloxane compound (A) is more regular, and the pattern collapse and bottom tailing are further suppressed, and the solvent resistance and preservation before hardening are further suppressed. Stability is even better.

In the method for synthesizing the polyoxyalkylene compound (A), when the tetrafunctional hydrolyzable decane compound is tetramethoxy decane and the trifunctional hydrolyzable decane compound is phenyltrimethoxy decane, the following reaction scheme can be carried out. Said.

In the above reaction scheme, Z ⁺ is a monovalent cation.

The compound (1) can be obtained by reacting the above tetramethoxynonane with a cation derived from a base and having a monovalent value represented by the above Z ⁺ in a solvent. The reaction was added to this solution by acid, and phenyl trimethoxy Silane, since the acid from H ^+, and the compound (1) of Z ⁺ is a hydrogen atom and silicon alkoxides. Thereby, the sterolized compound (1) is condensed with each other. At the same time, phenyltrimethoxydecane is substituted by hydrolysis and condensation, and the polymer represented by the above formula (2) is further obtained.

Further, in the above reaction scheme, phenyltrimethoxydecane may be added after the formation of the compound (1), or may be added to tetramethoxydecane. In this case, a compound (hereinafter, also referred to as "compound (1')") in which the group represented by X of the compound (1) is substituted with a phenyl group is formed, while the compound (1) is formed. Then, the compound (1) and the compound (1') are condensed by an acid to obtain a polymer represented by the above formula (2).

The lower limit of the polystyrene-equivalent weight average molecular weight (Mw) of the polyoxyalkylene compound (A) as measured by gel permeation chromatography (GPC) is preferably 800, preferably 1,000, and 1,200. good. On the other hand, the upper limit of the above Mw is 4,000, preferably 3,500, and preferably 3,200. When the above Mw is less than the above lower limit, there is a concern that the strength of the ruthenium containing film containing the polyoxy siloxane compound (A) is lowered. On the other hand, when the Mw exceeds the above upper limit, the uniformity of distribution of the specific oxane structure in the composition for forming a ruthenium-containing film may become difficult to increase.

Moreover, the Mw in this specification uses a GPC pipe string (for example, "G2000HXL 2 pieces, G3000HXL 1 piece of Tosoh Corporation, G4000HXL 1"), measured by a gel permeation chromatography (GPC) using monodisperse polystyrene at a flow rate of 1.0 mL/min, a solvent of tetrahydrofuran, and a column temperature of 40 °C. value.

The content of the polyoxyalkylene compound (A) in the composition for forming a ruthenium-containing film is usually 80% by mass or more, more preferably 85% by mass or more, and 90% by mass or more based on the total solid content. It is better. When the content of the polyoxyalkylene compound (A) is less than the above lower limit, the hardness of the formed ruthenium-containing film may be lowered. Further, in the present specification, "solid content" means a residue obtained by drying a sample on a hot plate at 175 ° C for 1 hour to remove volatile matter.

[solvent]

The solvent can be used without particular limitation as long as it can dissolve or disperse the polyoxyalkylene compound (A) and any component. Examples of the solvent include an alcohol solvent, an ether solvent, a ketone solvent, a guanamine solvent, an ester solvent, and an organic solvent such as a hydrocarbon solvent.

Examples of the alcohol-based solvent include aliphatic monoalcoholic solvents having a carbon number of 1 to 18 such as methanol, ethanol, propanol, methyl isobutyl ortho-ethanol, and n-hexanol; and carbon number of cyclohexanol or the like; ~18 alicyclic monool solvent; 1,2-propanediol and other polyvalent alcohol solvent having a carbon number of 3 to 18; propylene glycol monoethyl ether and other polyvalent alcohol partial ether solvent having a carbon number of 3 to 19 Wait.

Examples of the ether solvent include, for example, a di-aliphatic ether solvent such as diethyl ether, dipropyl ether or dibutyl ether; an aromatic cyclic ether solvent such as anisole or diphenyl ether; a cyclic ether such as tetrahydrofuran or dioxane; A solvent or the like.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, and methyl-iso-butyl ketone. a chain ketone solvent such as methyl-n-pentanone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-iso-butyl ketone, trimethyl fluorenone or acetophenone; A cyclic ketone solvent such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone or methylcyclohexanone; a diketone solvent such as 2,4-pentanedione or acetonylacetone; and the like.

Examples of the above amide-based solvent include N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, and N-methyl B. a chain amide-based solvent such as guanamine, N,N-dimethylacetamide or N-methylpropionamide; N-methylpyrrolidone, N,N'-dimethylimidazolidinone, etc. A cyclic amide-based solvent or the like.

Examples of the ester solvent include a monocarboxylic acid ester solvent such as n-butyl acetate or ethyl lactate; a lactone solvent such as γ-butyrolactone or valerolactone; and propylene glycol monomethyl ether B. a polyvalent alcohol moiety ether carboxylate solvent such as an acid ester; a polyvalent carboxylic acid diester solvent such as diethyl oxalate; A carbonate-based solvent such as dimethyl carbonate or diethyl carbonate.

Examples of the hydrocarbon-based solvent include n-pentane, iso-pentane, n-hexane, iso-hexane, n-heptane, iso-heptane, and 2,2,4-trimethylpentane. An aliphatic hydrocarbon solvent such as an alkane, n-octane, iso-octane, cyclohexane or methylcyclohexane; benzene, toluene, hydrazine, mesitylene, ethylbenzene, trimethylbenzene, methyl Aromatic hydrocarbons such as ethylbenzene, n-propylbenzene, iso-propylbenzene, diethylbenzene, iso-butylbenzene, triethylbenzene, di-iso-propylbenzene, n-pentylnaphthalene A solvent; a halogen-containing solvent such as dichloromethane, chloroform, chlorofluorocarbon, chlorobenzene or dichlorobenzene.

The solvent is preferably an alcohol solvent or an ester solvent, and a polyvalent alcohol partial ether solvent and a polyvalent alcohol monoalkyl ether acetate solvent are preferred, and propylene glycol monoethyl bromide is preferred. Alkyl ether and propylene glycol monomethyl ether acetate are more preferred. The solvent may be used singly or in combination of two or more.

The composition for forming a ruthenium-containing film may also contain water. When water is contained, since the polyoxyalkylene compound (A) is hydrated, the storage stability is improved. Moreover, when water is contained, the hardening of the film of the photoresist lower layer film can be accelerated, and a dense film can be obtained. When the composition for forming a ruthenium-containing film contains water, the lower limit of the content of water is preferably 0.1% by mass, more preferably 0.2% by mass. On the other hand, the upper limit of the content ratio is preferably 30% by mass, more preferably 20% by mass, and still more preferably 15% by mass. When the content of water exceeds the above upper limit, the storage stability of the composition for forming a ruthenium-containing film is obtained. It is lowered and the uniformity of the coating film is lowered.

[arbitrary ingredients]

Examples of the optional component which the compound for forming a ruthenium-containing film can contain include an acid generator, a nitrogen-containing compound, a β-diketone, a colloidal ruthenium dioxide, a colloidal alumina, an organic polymer, and an interfacial activity. Agent, alkali generator, and the like.

(acid generator)

The above acid generator is a component which generates an acid by exposure or heating. By containing the acid generator, the resin composition for forming a ruthenium film can effectively cause a crosslinking reaction between molecular chains such as a polyoxyalkylene compound (A) at a relatively low temperature including normal temperature.

An acid generator (hereinafter referred to as a "photoacid generator") which generates an acid by exposure, for example, is produced by the acid described in paragraphs [0077] to [0081] of JP-A-2004-168748. Agents, etc.

In addition, as an acid generator (hereinafter referred to as "thermal acid generator") which generates an acid by heating, the sulfonate-based acid generator exemplified as the photo-acid generator may be mentioned, for example. 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, alkylsulfonate, and the like.

The acid generator is preferably an osmium salt acid generator, preferably a sulfonium acid generator and a sulfonium acid generator, and triphenylsulfonium hexafluoro-n-butane-1-sulfonic acid is preferred. Ester, triphenylsulfonium 2-(adamantan-1-yl)-1,1-difluoroethane Alkyl-1-sulfonate, triphenylsulfonium adenyl-1-yloxycarbonyl-1,1-difluoromethanesulfonate, triphenylsulfonyl decane sultone-2-yloxycarbonyl Further preferred is -1,1-difluoromethanesulfonate and bis(t-butylphenyl)nonafluorobutanesulfonate.

The upper limit of the content of the acid generator is preferably 20 parts by mass, and preferably 10 parts by mass, based on 100 parts by mass of the polyoxyalkylene compound (A). One or two or more kinds of the acid generators can be used.

(nitrogen-containing compounds)

The nitrogen-containing compound is a compound having a basic amino group or a compound having a group which becomes a basic amino group by the action of an acid. The nitrogen-containing compound has an effect of improving the characteristics of the ashing resistance of the ruthenium-containing film obtained from the composition for forming a ruthenium film. This effect is considered to be due to the presence of a nitrogen-containing compound in the ruthenium-containing film, thereby promoting the crosslinking reaction in the ruthenium-containing film.

Examples of the nitrogen-containing compound include an amine compound, a guanamine-containing compound, a urea compound, and a nitrogen-containing heterocyclic compound.

Examples of the above amine compound include mono(cyclo)alkylamines; di(cyclo)alkylamines; tri(cyclo)alkylamines; substituted alkylanilines or derivatives thereof; ethylenediamine, N,N,N',N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-di Aminodiphenyl 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-amino group Phenyl)-2-(4-hydroxyphenyl)propane, 1,4-bis(1-(4-aminophenyl)-1-methyl Benzyl)benzene, 1,3-bis(1-(4-aminophenyl)-1-methylethyl)benzene, bis(2-dimethylaminoethyl)ether, bis(2- Diethylaminoethyl)ether, 1-(2-hydroxyethyl)-2-imidazolidinone, 2-quinoxalinol, N,N,N',N'-indole (2-hydroxypropyl) Ethylenediamine, N,N,N',N"N"-pentamethyldiethylenetriamine, and the like.

Examples of the above-mentioned amide group-containing compound include an Nt-butoxycarbonyl group-containing amine compound, an Nt-pentyloxycarbonyl group-containing amine compound, formamide, N-methylformamide, and N. , N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, acetamide, etc., benzamide, pyrrolidone, N-A Pyrrolidone, N-ethinyl-1-adamantylamine, isomeric cyanuric acid (2-hydroxyethyl), 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; pyrazine, pyrazole, pyridazine, quetiapine, guanidine, pyrrolidine, piperidine, piperidine ethanol, and 3-piperidin. Pyridyl-1,2-propanediol, morpholine, 4-methylmorpholine, 1-(4-indolyl)ethanol, 4-ethylmercaptomorpholine, 3-(N-morpholinyl)-1, 2-propanediol, 1,4-dimethylpiperazine, 1,4-dioxabicyclobicyclo[2.2.2]octane, and the like.

As the nitrogen-containing compound, among them, a guanamine-containing compound is preferred, and an N-t-butoxycarbonyl-containing amine compound and an N-t-pentyloxycarbonyl-containing amine compound are preferred.

From the viewpoint of making the shape of the pattern into a good one, the upper limit of the content of the nitrogen-containing compound is usually 100 parts by mass based on 100 parts by mass of the polyoxyalkylene compound (A). It is preferably 10 parts by mass, and preferably 1 part by mass, based on 30 parts by mass. The nitrogen-containing compound can be used alone or in combination of two or more.

<Modulation method of composition for forming a ruthenium film>

The composition for forming a ruthenium-containing film can be obtained by, for example, mixing an optional component with a polysiloxane compound (A), dissolving or dispersing it in a solvent. The lower limit of the solid content concentration of the composition for forming a ruthenium-containing film is preferably 0.5% by mass, and preferably 1% by mass. On the other hand, the upper limit of the solid content concentration is preferably 20% by mass, and preferably 10% by mass.

As described above, the composition for forming a ruthenium-containing film can suppress the pattern collapse and the bottom tail of the photoresist. Therefore, it can be suitably used as a pattern forming method and the like as a resist underlayer film formation.

<Graphic formation method>

The pattern forming method of the present invention has a step of forming a ruthenium-containing film on one surface of a substrate to be processed by using the composition for forming a ruthenium-containing film (hereinafter, also referred to as "the ruthenium-containing film formation step"); a step of forming a photoresist film on the above-mentioned ruthenium-containing film (hereinafter also referred to as "resist film formation step"); a step of exposing the photoresist film by light irradiation through a photomask (hereinafter also referred to as "exposure step"); forming a photoresist pattern by exposing the exposed photoresist film (hereinafter also referred to as "development step"); and using the above-mentioned photoresist pattern as a mask, and sequentially The step of dry etching the ruthenium-containing film and the substrate to be processed (hereinafter also referred to as "dry etching step"). Hereinafter, each step will be described.

[The film containing ruthenium formation step]

In the ruthenium-containing film formation step, the composition for forming a ruthenium-containing film is applied onto a substrate to be processed, and then, by heating, polysiloxane is cross-linked to form a ruthenium-containing film.

As the substrate to be processed, a conventionally known substrate such as a tantalum wafer or a wafer coated with aluminum can be used.

Examples of the coating method of the composition for forming a ruthenium-containing film include spin coating, cast coating, roll coating, and the like. Further, the film thickness of the formed ruthenium-containing film is usually 0.01 μm or more and 1 μm or less, and preferably 0.01 μm or more and 0.5 μm or less.

After coating the composition for forming a ruthenium-containing film, it is necessary to volatilize the solvent in the coating film by prebaking (PB). The temperature of PB is appropriately selected depending on the compounding composition of the composition for forming a ruthenium-containing film, and is usually 30 ° C or more and 200 ° C or less. Further, the time of the PB is usually 5 seconds or more and 600 seconds or less.

The lower limit of the heating temperature after application of the composition for forming a ruthenium-containing film is not particularly limited, and is preferably 100 ° C, more preferably 120 ° C, still more preferably 150 ° C, and particularly preferably 200 ° C. On the other hand, the upper limit of the above heating temperature is preferably 450 ° C, preferably 400 ° C, more preferably 300 ° C, and particularly preferably 240 ° C. The lower limit of the above heating time is preferably 10 seconds, preferably 15 seconds, more preferably 20 seconds, and particularly preferably 40 seconds. On the other hand, the upper limit of the above heating time is preferably 1 hour, 10 is preferred, 150 seconds is more preferred, and 80 seconds is particularly preferred. By forming a flaw When the heating temperature and time in the film are within the above range, the above-mentioned ruthenium-containing film can be formed simply and surely. Further, the environment during the heating is not particularly limited, and it may be in an air atmosphere or an inert gas atmosphere such as nitrogen.

Further, before the ruthenium-containing film formation step, a photoresist underlayer film of an organic film can be formed on the substrate to be processed, and the ruthenium-containing film can be formed on the photoresist underlayer film in the ruthenium-containing film formation step. In the multilayer photoresist process, the effect of the present invention can be more effectively exhibited by providing a photoresist underlayer film between the substrate to be processed and the ruthenium containing film. This photoresist underlayer film is usually formed by coating a composition for forming an organic underlayer film and drying it.

Further, an organic anti-reflection film can be formed on the substrate to be processed, and a ruthenium-containing film or the like can be formed thereon. As the anti-reflection film of the above-mentioned organic type, for example, those described in JP-A-6-12452 or JP-A-59-93448 can be used.

[Photoresist film forming step]

In the photoresist film forming step, a photoresist film is formed by coating a radiation sensitive resin composition on the underlayer film formed by the photoresist film forming step.

(sensing radiation resin composition)

The radiation sensitive resin composition contains a matrix polymer having an acid dissociable group, an acid generator, and a solvent. Further, the radiation sensitive resin composition may contain other components such as an acid diffusion controlling agent.

The above matrix polymer has an acid dissociable group. Acid dissociation The base refers to a group which is dissociated by an acid generated by an acid generator or the like. The acid dissociable group generates a polar group such as a carboxyl group on the matrix polymer by dissociation, thereby producing a difference in solubility between the exposed portion and the unexposed portion in the developing solution.

As the matrix polymer having the above acid-dissociable group, a polymer contained in the radiation-sensitive resin composition can be usually used to have a structure derived from 1-alkyl-1-cycloalkyl (meth) acrylate. a polymer, a polymer having a structure derived from 2-cycloalkylpropan-2-yl (meth) acrylate, having a structure derived from 2-alkyl-2-adamantyl (meth) acrylate A polymer, and a polymer having a structure derived from 2-(adamantan-1-yl)propan-2-yl (meth) acrylate.

Further, the matrix polymer may have a structure such as a lactone structure, a cyclic carbonate structure, or a sultone structure. By having such a structure, the solubility of the photoresist film to the developing liquid can be further improved.

The lower limit of the content of the matrix polymer in the total solid content of the radiation sensitive resin composition is preferably 70% by mass, more preferably 75% by mass, and still more preferably 80% by mass.

The form of the acid generator is, for example, a form of a low molecular compound, a form in which the low molecular compound is introduced into one part of the polymer, and a form of both of them. The low molecular weight compound is, for example, the same as the acid generator exemplified in the composition for forming a ruthenium-containing film. Among these, a ruthenium chloride compound is preferred, and a phosphonium salt and a tetrahydrothiophene sulfonium salt are preferred.

When the acid generator is the above-mentioned low molecular compound, from the viewpoint of ensuring sensitivity and development of the above-mentioned radiation sensitive resin composition, The lower limit of the content of the acid generator of 100 parts by mass of the matrix polymer is preferably 0.1 part by mass, preferably 0.5 part by mass, more preferably 1 part by mass, and particularly preferably 3 parts by mass. On the other hand, the upper limit of the above content is preferably 30 parts by mass, more preferably 20 parts by mass, still more preferably 15 parts by mass, and particularly preferably 15 parts by mass. When the content of the acid generator is within the above range, the sensitivity and developability of the radiation sensitive resin composition are improved. One or two or more kinds of the acid generators can be used.

The solvent is, for example, the same as the solvent exemplified in the composition for forming a ruthenium-containing film. Among these, an ester solvent and a ketone solvent are preferred, and propylene glycol monomethyl ether acetate and cyclohexanone are preferred. The solvent can be used alone or in combination of two or more.

The acid diffusion controlling agent is, for example, the same as the nitrogen-containing compound exemplified in the composition for forming a ruthenium-containing film, and a photocrackable base.

The photocrackable base is a compound which generates a weak acid by exposure, and functions as an acid trapping function by an anion in an unexposed portion to function as a quencher, and further captures an acid diffused from the exposed portion. On the other hand, an acid is generated in the exposed portion and the anion is destroyed, so that the acid trapping function is not obtained. That is, since it acts as a quencher only in the unexposed portion, the contrast of the dissociation reaction of the acid dissociable group is improved. Examples of the photocrackable base include a ruthenium chloride compound which decomposes by exposure and loses acid diffusion controllability. Examples of the ruthenium chloride compound include a ruthenium chloride compound and a ruthenium chloride compound.

Acid diffusion control agent is preferably photo-disinfecting base, triphenyl Alkaloid, and triphenyl camphorsulfonate are preferred.

When the acid diffusion controlling agent is an acid diffusion controlling agent, the lower limit of the content of the acid diffusion controlling agent relative to 100 parts by mass of the matrix polymer is preferably 0.1 part by mass, and preferably 0.3 part by mass. On the other hand, the upper limit of the above content is preferably 10 parts by mass, more preferably 7 parts by mass, and still more preferably 5 parts by mass. When the content of the acid diffusion controlling agent exceeds the above upper limit, the sensitivity of the radiation-sensitive linear resin composition may be lowered. The acid diffusion inhibitor may be used singly or in combination of two or more.

As a coating method of the above-mentioned radiation sensitive resin composition, for example, the same as those exemplified in the above-described ruthenium-containing film forming step can be used. Further, the film thickness of the formed photoresist film is usually 0.01 μm or more and 1 μm or less, and preferably 0.01 μm or more and 0.5 μm or less.

Further, after applying the above-mentioned radiation sensitive resin composition, the solvent in the coating film may be volatilized by prebaking (PB) as necessary. The temperature and time of PB can be set to be the same as the PB in the above-mentioned ruthenium-containing film.

Further, in order to prevent the influence of alkaline impurities and the like contained in the environmental atmosphere, a protective film may be provided on the formed photoresist film. The protective film is described in, for example, Japanese Laid-Open Patent Publication No. Hei 5-188598. In addition, a liquid immersion protective film described in, for example, JP-A-2005-352384, etc., can be provided on the photoresist film in order to prevent the acid generator from flowing out of the photoresist film. Moreover, these technologies can also be used together.

[Exposure step]

In this step, the photoresist film formed in the above-described photoresist film forming step is exposed. As this exposure, for example, an isolated trench pattern can be formed by performing a reduced projection exposure via an isolation line pattern mask on a desired field. Further, the exposure may be performed twice or more depending on the desired pattern of the rain mask. When the exposure is performed twice or more, the exposure system is preferably carried out continuously. When performing multiple exposures, the first reduced projection exposure is performed via the line width and the line pattern mask in the desired field, and then the exposure portion to which the first exposure is applied is performed so that the lines can be crossed. 2 Reduce the projection exposure. It is preferable that the first exposure portion and the second exposure portion are orthogonal to each other. By making them orthogonal, it becomes easy to form a true circular contact hole pattern on the unexposed portion surrounded by the exposed portion.

Examples of the liquid immersion liquid used for the exposure include water or a fluorine-based inactive liquid. The liquid immersion liquid is preferably a liquid which is transparent to the exposure wavelength and which can control the skew of the optical image projected on the film to a minimum and the temperature coefficient of the refractive index is as small as possible, especially when the exposure light source is an ArF excimer. In the case of light emission (wavelength: 193 nm), in addition to the above-described viewpoints, it is preferable to use water from the viewpoint of ease of handling and ease of handling. When water is used, in order to reduce the surface tension of water, it is also possible to add an additive which increases the interfacial activity in a slight proportion. This additive is preferably a cloth that dissolves the photoresist layer on the wafer and can ignore the effects on the optical coating under the lens. The water used is preferably distilled water.

The radiation used in the exposure is in response to the above-mentioned radiation. The type of the acid-generating material to be contained in the resin composition is appropriately selected, and examples thereof include electromagnetic waves such as ultraviolet rays, far ultraviolet rays, visible light, EUV, X-rays, and γ-rays, and charged particle lines such as electron beams and α lines. Among them, far ultraviolet rays, EUVs, and electron lines are preferable, and ArF excimer laser light (wavelength 193 nm), KrF excimer laser light (wavelength 248 nm), EUV, and electron lines are preferable. The exposure conditions such as the amount of exposure are appropriately selected depending on the composition of the radiation-sensitive resin composition, the type of the additive, and the like. In the pattern forming method, there may be a plurality of exposure steps. In this case, the same light source may be used for the plurality of exposure systems, and a different light source may be used.

Further, it is preferred to perform post-exposure baking (PEB) after exposure. By performing PEB, the dissociation reaction of the acid dissociable group in the above radiation sensitive resin composition can be smoothly carried out. The PEB temperature is usually 30 ° C or more and 200 ° C or less, preferably 50 ° C or more and 170 ° C or less, and preferably 70 ° C or more and 120 ° C or less. The PEB time is usually 5 seconds or more and 600 seconds or less, and preferably 10 seconds or more and 300 seconds or less.

[development step]

In this step, the exposed photoresist film in the above exposure step is developed using a developing solution, and subjected to a drying treatment or the like. Thereby, a prescribed photoresist pattern can be formed.

In the case of alkali development, examples of the developing solution used for the above-mentioned development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, and n. -propylamine, diethylamine, Di-n-propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), pyrrole, piperidine, choline, 1, a base made of at least one of a basic compound such as 8-dicyclic bicyclobicyclo-[5.4.0]-7-undecene, 1,5-diindole bicyclo-[4.3.0]-5-nonene or the like Aqueous solution, etc. Among them, an aqueous TMAH solution is preferred, and a 2.38 mass% TMAH aqueous solution is preferred.

In addition, in the case of the development of the organic solvent, an organic solvent such as a hydrocarbon solvent, an ether solvent, an ester solvent, a ketone solvent, or an alcohol solvent can be used. The above-mentioned organic solvent is, for example, one or two or more kinds of solvents exemplified as the solvent of the above-mentioned composition for forming a ruthenium-containing film. Among these, an ester solvent or a ketone solvent is also preferred. The ester solvent is preferably an acetate solvent, and n-butyl acetate is preferred. The ketone solvent is preferably a chain ketone, and 2-heptanone is preferred. The lower limit of the content of the organic solvent in the developing solution is preferably 80% by mass, preferably 90% by mass, more preferably 95% by mass, and particularly preferably 99% by mass.

A suitable amount of surfactant can be added to the developing solution as necessary. As the surfactant, for example, an ionic or nonionic fluorine-based and/or a lanthanoid surfactant can be used.

As a developing method, for example, a method of immersing a substrate in a tank filled with a developing liquid for a certain period of time (dipping method), and floating the developing liquid by surface tension on the surface of the substrate for a predetermined period of time can be used. Method for developing image (liquid method), method for spraying developing liquid on substrate surface (spray method), scanning liquid at a certain speed on a substrate rotating at a certain speed A method of applying a nozzle while continuously discharging a developing liquid (dynamic dispensing method) or the like.

After the above development, it is preferred to wash the formed photoresist pattern with a rinsing liquid. As the rinsing liquid, water is preferred for alkali development, and pure water is preferred. In the case of organic solvent development, an alcohol solvent or an ester solvent is preferred, and an alcohol solvent having a carbon number of 6 to 8 is preferred, and 1-hexanol, 2-hexanol, 2-heptanol, and A are used. The isobutyl butyl alcohol is more preferred.

Examples of the method of the cleaning treatment include a method of continuously discharging a rinse liquid on a substrate that is rotated at a constant speed (a spin coating method), and a method of immersing the substrate in a tank filled with a rinse liquid for a predetermined period of time ( Dipping method), a method of spraying a scouring liquid on the surface of a substrate (spraying method), or the like.

[dry etching step]

In the dry etching step, the photoresist pattern after the developing step is used as a mask, and the germanium-containing film is dry-etched to form a germanium-containing pattern. Thereafter, the ruthenium-containing pattern is used as a mask, and the substrate to be processed is dry etched to form a pattern on the substrate to be processed.

This dry etching can be carried out using a known dry etching apparatus. Further, the etching gas system used for dry etching can be appropriately selected depending on the elemental composition of the ruthenium-containing film to be etched, and examples thereof include CHF ₃ , CF ₄ , C ₂ F ₆ , C ₃ F ₈ , SF ₆ and the like. a fluorine-based 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, a gas such as H ₂ , NH ₃ , CO or CO ₂ , He, N ₂ or Ar Inert gas, etc. These gas systems can be used alone or in combination of two or more.

The etching gas system used for the etching of the ruthenium film is a fluorine-based gas Preferably, it is preferred to mix an oxygen-based gas and an inert gas with a fluorine-based gas. The etching gas system used for etching the substrate to be processed is preferably an oxygen-based gas, and it is preferable to mix an inert gas with an oxygen-based gas.

Further, in the case where the photoresist underlayer film is formed, the dry etching step etches the photoresist underlayer film using the ruthenium-containing pattern as a mask, and thereafter etches the substrate to be processed. The etching gas system used for etching the photoresist underlayer film is preferably an oxygen-based gas, and it is preferable to mix an inert gas with an oxygen-based gas.

[Examples]

Hereinafter, the present invention will be described in detail based on the examples, but the present invention is not limited by the examples. The measurement methods of various physical property values are as follows.

[Mw and Mn measurement]

The Mw and Mn of the polyoxyalkylene compound were measured by gel permeation chromatography (GPC) by the following conditions.

Pipe column: 2 pieces of "G2000HXL" from Tosoh Corporation, 1 "G3000HXL" and 1 "G4000HXL"

Dissolution solvent: tetrahydrofuran

Column temperature: 40 ° C

Flow rate: 1.0mL/min

Detector: differential refractometer

Reference material: monodisperse polystyrene

[ ²⁹ Si-NMR analysis]

2.4 g of each resin solution obtained in Examples 1 to 6 and Comparative Example 1 and chromium (III) of ginseng (2,4-pentanedionate) were dissolved in 1.0 g of heavy benzene as a sample, and used. A nuclear magnetic resonance apparatus (Bruker BioSpin Co., Ltd.) performed ²⁹ Si-NMR measurement of the above sample. According to the difference in the chemical shifts of the respective spectra obtained by the ²⁹ Si-NMR measurement, the integral value of the signal provided by the germanium atom contained in the specific alkoxysilane structure is determined from the germanium atom possessed by the polyoxyalkylene compound. The ratio Q (%) of the sum of the integrated values of the signals provided. Further, the values of S1 to S4 represented by the following formulas (III) to (VI) are obtained.

S1=(q1/q1+q2+q3+q4)×100 (III)

S2=(q2/q1+q2+q3+q4)×100 (IV)

S3=(q3/q1+q2+q3+q4)×100 (V)

S4=(q4/q1+q2+q3+q4)×100 (VI)

(In the above formulae (III) to (VI), q1 to q4 are synonymous with the above formula (I).)

<Synthesis of polyoxyalkylene compounds>

The oxirane compound was separately synthesized according to the following method. The compounds used in the synthesis of the polyoxyalkylene compound are as follows.

[hydrolyzable decane compound]

M-1: tetramethoxy decane (compound represented by the following formula M-1)

M-2: phenyltrimethoxydecane (compound represented by the following formula M-2)

M-3: 4-methylphenyltrimethoxydecane (compound represented by the following formula M-3)

M-4: methyltrimethoxydecane (compound represented by the following formula M-4)

M-5: 2-[3-(trimethoxyindolyl)propyl]anhydrosuccinic acid (the following formula Compound shown by M-5)

[catalyst]

S-1: tetramethylammonium hydroxide

S-2: tetrabutylammonium hydroxide

S-3: Oxalic acid dihydrate

[Example 1]

[Synthesis of polyoxyalkylene compound (A-1)]

12.86 g of the catalyst (S-1) was dissolved in 38.57 g of water by heating to prepare an aqueous solution. Next, 51.42 g of this aqueous solution and 13.46 g of methanol were placed in a flask, and a cooling tube and a compound (M-) were placed in the flask. 1) A dropping funnel of 30.67 g and a compound (M-2) of 4.44 g. Thereafter, the flask was heated to 40 ° C in an oil bath, and the compound (M-1) and the compound (M-2) were slowly dropped from the dropping funnel, and reacted at 60 ° C for 4 hours. After completion of the reaction, the flask containing the reaction solution was cooled to 10 ° C or lower. Here, 77.56 g of an aqueous maleic acid solution obtained by dissolving anhydrous maleic acid 16.60 in 60.96 g of water was prepared and cooled to 10 ° C or lower. Next, the above reaction solution was dropped into the aqueous maleic acid solution and stirred at 10 ° C or lower for 30 minutes. To the stirred reaction solution, 177.56 g of 1-butyl alcohol was added and transferred to a separatory funnel, and 355.11 g of water was added thereto, and the mixture was washed three times with water. The water-washed reaction solution was transferred to a flask, and the flask was further charged with 177.56 g of propylene glycol-1-ethyl ether. Thereafter, the flask was placed on an evaporator to remove 1-butanol to obtain 71.02 g of a resin solution. The solid content in the resin solution was defined as a polyoxyalkylene compound (A-1). The content ratio of the solid content in the obtained resin solution was 15.0% by mass. Further, the weight average molecular weight (Mw) of the polyoxyalkylene compound (A-1) was 3,100, and the value of Q was 86%, and the values of S1 to S4 were 0%, 13%, 60%, and 27%, respectively. Further, the value of q represented by the following formula (I) is 0.13, and the value of q' represented by the following formula (II) is 0.27.

q=(q1+q2)/(q1+q2+q3+q4) (I)

q’=(q4)/(q1+q2+q3+q4) (II)

[Embodiment 2]

[Synthesis of polyoxyalkylene compound (A-2)]

12.86 g of the catalyst (S-1) was heated and dissolved in 38.57 g of water to adjust to an aqueous solution. Next, 51.42 g of this aqueous solution and 13.46 g of methanol were placed in a flask, and a cooling tube and a compound (M-) were placed in the flask. 1) A dropping funnel of 30.67 g. Thereafter, the flask was heated to 40 ° C in an oil bath, and the compound (M-1) was slowly dropped from the dropping funnel, and allowed to react at 60 ° C for 4 hours. Then, a dropping funnel containing 4.44 g of the compound (M-2) was placed in a flask, and the compound (M-2) was slowly dropped, and allowed to react at 60 ° C for 2 hours. After completion of the reaction, the flask containing the reaction solution was cooled to 10 ° C or lower. Here, 77.56 g of an aqueous maleic acid solution in which 16.60 g of anhydrous maleic acid was dissolved in 60.96 g of water was prepared and cooled to 10 ° C or lower. Next, the above reaction solution was dropped into the aqueous maleic acid solution, and stirred at 10 ° C or lower for 30 minutes. To the stirred reaction solution, 1-butyl alcohol 177.56 was added and transferred to a separatory funnel, and 355.11 g of water was added thereto, and the mixture was washed with water three times. The water-washed reaction solution was transferred to a flask, and 177.56 g of propylene glycol-1-ethyl ether was further added to the flask. Thereafter, the flask was placed on an evaporator, and 1-butanol was removed to obtain 71.02 g of a resin solution. The solid content in the resin solution was defined as a polyoxyalkylene compound (A-2). The content ratio of the solid content in the obtained resin solution was 14.0% by mass. Further, the polyoxymethane compound (M-2) had a weight average molecular weight (Mw) of 2,700, a Q value of 84%, and S1 to S4 values of 1%, 10%, 66%, and 23%, respectively. Further, the value of q represented by the above formula (I) is 0.11, and the value of q' represented by the above formula (II) is 0.23.

[Examples 3 to 11]

[Synthesis of polyoxyalkylene compounds (A-3) to (A-11)]

In the same manner as in Example 1, except that each compound and catalyst used in the types and amounts shown in Table 1 below were used, the polyoxyalkylene was synthesized. Compound (A-3) ~ (A-11). The content ratio of the solid content in the resin solution obtained in each of the examples, and the values of Mw and Q of the polyoxyalkylene compound, the values of S1 to S4, the value of q, and the value of q' are shown in Table 1. And Table 2.

[Comparative Example 1]

[Synthesis of polyoxyalkylene compound (CA-1)]

1.28 g of a catalyst (S-3) was heated and dissolved in 12.85 g of water to prepare a catalyst aqueous solution. Next, 25.05 g of the compound (M-1), 3.63 g of the compound (M-2), and 57.19 g of propylene glycol monoethyl ether were placed in a flask, and the flask was equipped with a cooling tube and a dropping solution with an aqueous solution of a catalyst. funnel. Thereafter, the flask was heated to 60 ° C in an oil bath, and the aqueous catalyst solution was slowly dropped from the dropping funnel, and allowed to react at 60 ° C for 4 hours. After completion of the reaction, the flask containing the reaction solution was cooled, and then placed on an evaporator to remove methanol formed by the reaction, and then 97.3 g of a resin solution was obtained. The solid content in the resin solution was changed to a polyoxyalkylene compound (CA-1). The content ratio of the solid content in the obtained resin solution was 18.0% by mass. Further, the obtained polyoxyalkylene compound (CA-1) had a weight average molecular weight (Mw) of 2,000, a value of Q of 90%, and values of S1 to S4 of 3%, 25%, 54% and 18%, respectively. Further, the value of q represented by the above formula (I) is 0.28, and the value of q' represented by the above formula (II) is 0.18.

<Preparation of composition containing ruthenium film formation>

The components used in the preparation of the composition for forming a ruthenium film are as follows.

[acid generator]

B-1: a compound represented by the following formula (B-1)

B-2: a compound represented by the following formula (B-2)

B-3: a compound represented by the following formula (B-3)

[solvent]

C-1: propylene glycol monoethyl ether

C-2: propylene glycol monomethyl ether acetate

[Embodiment 12]

1.3 parts by mass of (A-1) as a polyoxyalkylene compound, (B-1) 0.06 parts by mass as an acid generator, and (C-1) 93.11 parts by mass and (C-2) 4.90 as a solvent. The mixture was filtered through a 0.2 μm membrane filter to obtain a composition for forming a ruthenium-containing film (L-1).

[Examples 13 to 31 and Comparative Examples 2 to 4]

In the same manner as in Example 12, except that each of the compounds of the type and the amount of use shown in the following Table 3 was used, the composition for forming a ruthenium-containing film (L-2) to (L-20) and CL-1)~(CL-3).

<Manufacture of Substrate for Evaluation>

[Modulation of Radiation-Sensitive Resin Composition (J-1)]

The individual systems used in the synthesis of the polymers (R-1) and (R-2) are shown below.

(Synthesis of polymer (R-1))

Preparation of Compound (r-1) 4.0 g (10 mol%), Compound (r-2) 14.8 g (40 mol%), (r-3) 5.1 g (10 mol%), and Compound (r-5) 19.5 g ( After dissolving 60 g of 2-butanone, 40 g of azobisisobutyronitrile (AIBN) was added to the monomer solution. On the other hand, after a 30-mL nitrogen purge of a 200 mL three-necked flask charged with 30 g of 2-butanone, the reaction vessel was stirred and heated to 80 ° C at the same time, and the previously prepared monomer solution was used for 3 hours using a dropping funnel. Drop in. The start of the dropping time was set as the polymerization start time, and the polymerization reaction was carried out for 6 hours. After completion of the polymerization, the solution was cooled to 30 ° C or lower by a water-cooled polymerization solution, and 600 g of methanol was charged, and the precipitated white powder was separated by filtration. The white powder which was separated by filtration was washed twice in a slurry of 150 g of methanol, and then separated by filtration, and dried at 50 ° C for 17 hours to obtain a copolymer of a white powder. The obtained copolymer had Mw of 12,000, Mw/Mn of 1.5, and a yield of 50%. Further, as a result of ¹³ C-NMR analysis, a structural unit derived from the compound (r-1): a structural unit derived from the compound (r-2): a structural unit derived from the compound (r-3): derived from a compound ( The content ratio (mol%) of the structural unit of r-5) is 11:38:10:41. This copolymer was designated as a polymer (R-1). Further, ¹³ C-NMR analysis was carried out using JNM-ECX400 manufactured by JEOL Ltd. using heavy chloroform as a measuring solvent. The content ratio of each structural unit of the polymer is calculated from the area ratio of the peaks corresponding to the respective structural units in the spectrum obtained by ¹³ C-NMR.

(Synthesis of polymer (R-2))

60.7 g (60 mol%) of the compound (r-4), 33.1 g (25 mol%) of the compound (r-6), and 18.8 g (15 mol%) of the compound (r-7) were dissolved in 100 g of 2-butanone to obtain a solution. Solution. To the obtained dissolved solution, 3.7 g of azobisisobutyronitrile (AIBN) was charged to prepare a monomer solution. Next, a 500-mL three-necked flask containing 100 g of 2-butanone was subjected to nitrogen purge for 30 minutes. After the nitrogen purge, the reaction vessel was stirred and heated to 80 ° C, and the above-mentioned monomer solution prepared beforehand was dropped into the above-mentioned three-necked flask over 3 hours using a dropping funnel. The start time of the dropwise addition was set as the polymerization start time, and the polymerization reaction was carried out for 6 hours to obtain a polymerization solution. After completion of the polymerization, the mixture was cooled to 30 ° C or lower by a water-cooled polymerization solution, and then 800 g of methanol/water = 19/1 was introduced to precipitate a white substance. After removing the supernatant solution, it was washed with 800 g of methanol/water = 19/1. Thereafter, solvent substitution was carried out with propylene glycol monomethyl ether to obtain a solution of the polymer (R-2) (yield 66%). This copolymerization The molecular weight (Mw) of the material was 6,700, Mw/Mn was 1.6, and the result of 13C-NMR analysis was derived from the structural unit of the compound (r-4): the structural unitization derived from the compound (r-6): derived from the compound The content ratio (mol%) of the structural unit of (r-7) was 62:23:15.

The components used in the preparation of the radiation sensitive resin composition (J-1) are as follows.

(acid generator)

B-1: a compound represented by the following formula (b-1)

(acid diffusion control agent)

(d-1): a compound represented by the following formula (d-1)

(solvent)

(e-1): propylene glycol monomethyl ether acetate

(e-2): cyclohexanone

(e-3): γ-butyrolactone

100 parts by mass of the mixed polymer (R-1), 3 parts by mass of the polymer (R-2), 10 parts by mass of the acid generator (b-1), 1.4 parts by mass of the acid diffusion controlling agent (d-1), and a solvent (e-1) 2,185 parts by mass, 935 parts by mass of the solvent (e-2), and 30 parts by mass of the solvent (e-3), and the mixture was filtered using a 0.2 μm membrane filter to prepare a radiation-sensitive resin composition. (J-1).

[Formation of ruthenium containing film]

An anti-reflective film forming material ("HM8006" of JSR Co., Ltd.) was applied onto a 12-inch wafer surface by a spin coater ("CLEAN TRACK ACT12" of Tokyo Electronics Co., Ltd.), and heated at 250 ° C for 60 seconds. An antireflection film having a film thickness of 100 nm was formed. Coating the composition for forming a ruthenium-containing film on the surface of the anti-reflection film by using the above-described spin coater, After heating at 220 ° C for 1 minute using a hot plate, it was cooled at 23 ° C for 60 seconds to form a ruthenium-containing film having a film thickness of 30 nm. The film thickness measurement of this ruthenium film was measured using a film thickness measuring device ("M-2000D" by J.A. Woollam Co., Ltd.).

[Formation of photoresist pattern]

The radiation sensitive resin composition (J-1) was applied onto the surface of the above-mentioned ruthenium-containing film by the above-mentioned spin coater, heated at 90 ° C for 60 seconds, and then cooled at 23 ° C for 30 seconds to form a film thickness of 100 nm. Photoresist film. Next, an ArF immersion exposure apparatus ("S610C" of NIKON Co., Ltd.) was used to form a mask of a mask size through a 40 nm line width/80 nm pitch under an optical condition of NA: 1.30 and Dipole, and the photoresist was exposed. membrane. After the exposure, a photoresist coating developing device ("CLEAN TRACK Lithius Pro-i" by Tokyo Electronics Co., Ltd.) was used, and PEB was dried at 100 ° C for 60 seconds, and cold at 30 ° C for 30 seconds. Thereafter, butyl acetate was developed for 30 seconds at 23 ° C, followed by rinsing with methyl isobutyl orthoester (MIBC) for 10 seconds. After rinsing, a photoresist pattern of 40 nm line width/80 nm pitch was formed by spin drying at 2000 rpm for 15 seconds.

<evaluation>

According to the method described below, the pattern collapse resistance and the pattern shape of each of the composition for forming a ruthenium-containing film were evaluated by measuring the above-described formed photoresist pattern. In addition, the length measurement and observation of the resist pattern are performed using a scanning electron microscope ("CG-4000" by Hitachi High-Tech Co., Ltd.).

[Graphic collapse resistance]

In the formation of the above-described photoresist pattern, an exposure amount of a pattern in which a line width of a line is 38 nm and a distance (line distance) between adjacent lines is 40 nm is set as an optimum exposure amount. Using this optimum exposure as a reference, the exposure is measured stepwise and the exposure is performed sequentially, and the obtained line width is measured. As the exposure amount decreases and the line width of the pattern becomes smaller, and the line width becomes smaller than a certain value, the collapse of the photoresist pattern is observed. Here, the line width corresponding to the minimum exposure amount in which the resist pattern collapse is not found is defined as the minimum pre-collapse size (nm), and is taken as an index of the pattern collapse resistance. The pattern collapse resistance is evaluated as "A" when the size before the minimum collapse is 32 nm or less, "B" when it exceeds 32 nm and 38 nm or less, and "C" when it exceeds 38 nm. In the above evaluation, A and B are considered as qualified. The results of this evaluation are shown in Table 4.

[Shape shape]

The shape of the pattern will be rated as "A" when there is no bottom tail on the photoresist pattern, and "C" when there is a pattern collapse or bottom tail. In the above evaluation, A is considered as a qualified person. The results of this evaluation are shown in Table 4.

[Solvent resistance of uncured film]

Moreover, each of the composition for forming a ruthenium-containing film prepared in the above examples and comparative examples was applied onto the surface of a 12-inch wafer by using a spin coater ("CLEAN TRACK ACT12" by Tokyo Electronics Co., Ltd.). Allow to stand at room temperature for 30 minutes. Next, a thinner ("OK73 thinner" of Tokyo Ohka Kogyo Co., Ltd.) was applied to the surface of the coated composition for forming a ruthenium-containing film, and after standing for 30 seconds, the diluent was removed. The thickness of the composition for forming a ruthenium-containing film before and after the application of the thinner was measured using a high-speed spectroscopic ellipsometer ("M-2000" by JA Woollam Co., Ltd.), and the thickness (T ₀ ) before coating and the coating were determined. The difference in thickness (T) after the cloth (T ₀ -T), the ratio ((T ₀ -T)/T ₀ ) of the above difference with respect to the thickness before coating was used as an index of the solvent resistance of the uncured film. When the above ratio is more than 80%, it is rated as "A", when it is more than 60% and 80% or less, it is rated as "B", and when it is 60% or less, it is rated as "C". In the above evaluation, A and B are considered as qualified.

[Save stability]

Further, the ruthenium-containing film-forming composition prepared in the above Examples and Comparative Examples was heated at 40 ° C for one week. The weight average molecular weight of the ruthenium-containing film-forming composition before and after heating is measured, and the difference between the molecular weight after heating (Mw _h ) and the initial molecular weight (Mw ₀ ) (Mw _{h -} Mw ₀ ) is determined, which is relative to the initial stage. The ratio of the above difference in molecular weight ((Mw _{h -} Mw ₀ ) / Mw ₀ ) is used as an indicator of preservation stability. If the ratio is 20% or less, it is rated as "A", when it is more than 20% and 30% or less, it is rated as "B", and when it is more than 30%, it is rated as "C". In the above evaluation, A and B are considered as qualified.

As shown in Table 4, when the ruthenium-containing film containing the composition for forming a ruthenium film of the example was used, the pattern collapse resistance was excellent, and the bottom tail of the pattern was also reduced. On the other hand, the ruthenium-containing films of the comparative examples were all inferior in pattern collapse resistance, and there was a tendency to easily cause tail smearing of the pattern.

Further, the composition for forming a ruthenium-containing film of the examples is excellent in solvent resistance and storage stability in an unhardened state. On the other hand, the composition for forming a ruthenium-containing film of the comparative example was inferior in solvent resistance in an uncured state, and was also inferior in storage stability.

[Industrial availability]

The composition for forming a ruthenium-containing film according to the present invention, the pattern forming method, and the polyoxyalkylene compound have high storage stability, and can suppress pattern in a multilayer photoresist process, particularly in organic solvent development. The bottom of the collapse and the photoresist is tailed, and the solvent resistance before hardening is excellent. Therefore, these can be suitably used for pattern formation in semiconductor device manufacturing and the like which are expected to be further miniaturized in the future.

Claims (10)

A composition for forming a ruthenium film, which comprises a polysiloxane compound and a solvent; and the polyoxy siloxane compound has a structure represented by the following formulas (Q1) to (Q4), and has (Q2) The structure represented by the structure, the structure represented by (Q3), and the structure represented by (Q4), and the signals obtained by ²⁹ Si-NMR are represented by the following formulas (Q1) to (Q4). When the integrated value of the signal supplied by each of the germanium atoms in the structure is q1 to q4, the value of q calculated by the following formula (I) is 0.25 or less, and the weight average molecular weight is 4,000 or less; q=(q1+ Q2)/(q1+q2+q3+q4) (I) In the formulae (Q1) to (Q4), each of R is independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms; however, R is a group which does not contain a deuterium atom; * represents a site bonded to a deuterium atom. The composition for forming a ruthenium-containing film according to claim 1, wherein the value of the above q is 0.2 or less. The composition for forming a ruthenium-containing film according to claim 2, wherein the value of q is 0.15 or less. For the formation of the ruthenium film of claim 1, request 2 or claim 3 a composition in which the value of q' calculated by the following formula (II) is 0.2 or more; q'=(q4)/(q1+q2+q3+q4) (II) in the formula (II), q1 to q4 It is synonymous with the above formula (I). The composition for forming a ruthenium-containing film according to claim 4, wherein the value of q' is 0.25 or more. The composition for forming a ruthenium-containing film according to any one of Claims 1 to 5, wherein the ruthenium atom in the structure represented by the above formulas (Q1) to (Q4) has the entire ruthenium oxyalkylene compound. The ratio of ruthenium atoms is 50 mol% or more. The composition for forming a ruthenium-containing film according to any one of Claims 1 to 6, wherein the polyoxy siloxane compound is obtained by condensing a compound represented by the following formula (1) by using an acid. ; In the formula (1), X is -O ^- Z ⁺ or a monovalent organic group having 1 to 20 carbon atoms; and Z ⁺ is a monovalent cation. The composition for forming a ruthenium-containing film according to any one of claims 1 to 7, which is a member for forming a photoresist underlayer film. A pattern forming method characterized by the following steps: a step of forming a ruthenium-containing film on one surface of a substrate to be processed, using a composition for forming a ruthenium-containing film according to claim 8, and a step of forming a photoresist film on the ruthenium-containing film using a photoresist composition; a step of exposing the photoresist film to light exposure of the photomask; developing the exposed photoresist film to form a photoresist pattern; and using the photoresist pattern as a mask to sequentially dry the ruthenium containing film And the step of processing the substrate as described above. A polyoxane compound having a structure represented by (Q2), a structure represented by (Q3), and a structure represented by (Q4) among the structures represented by the following formulas (Q1) to (Q4). Among the signals obtained by ²⁹ Si-NMR, when the integral value of the signal supplied from each of the germanium atoms in the structures represented by the following formulas (Q1) to (Q4) is q1 to q4, the following The value of q calculated by the formula (I) is 0.25 or less, and the weight average molecular weight is 4,000 or less; q=(q1+q2)/(q1+q2+q3+q4) (I) In the formulae (Q1) to (Q4), R each independently represents a hydrogen atom or an organic group having a monovalent number of carbon atoms of 1 to 20. However, R is a person who does not contain a helium atom. * indicates that the bond is bonded to the atom of the atom.