JP5970933B2 - Pattern formation method - Google Patents

Description

  The present invention relates to a pattern forming method.

  In the field of manufacturing semiconductors and the like, miniaturization of processing size using a multilayer resist process is progressing in order to obtain a higher degree of integration. In this multilayer resist process, after forming an inorganic film using an inorganic material on a substrate to be processed, a resist film having a different etching selectivity from the inorganic film is formed on the inorganic film using a resist composition, and then The mask pattern is transferred by exposure and developed with a developer to obtain a resist pattern. Subsequently, the resist pattern is transferred to an inorganic film by dry etching, and the pattern of the inorganic film is finally transferred to a substrate to be processed to obtain a substrate on which a desired pattern is applied.

  In this multilayer resist process, in order to process a substrate to be processed more finely, the resist film is being made thinner. Therefore, a film having a higher etching selection ratio is demanded as the inorganic film, and the use of a metal-containing film has been studied (Japanese Patent Laid-Open Nos. 2000-275820 and 2002-343767 and International Publication). No. 2006/40956).

  However, when such a metal-containing film is used in a multilayer resist process, when the resist film on the metal-containing film is developed with an alcal developer, the metal is eluted from the metal-containing film into the alkali developer, and the developing device Cause pollution. In addition, when a resist film is formed on the metal-containing film by applying a resist composition, a metal component may be eluted from the metal-containing film into the resist film. If the metal component is eluted into the resist film, it may cause development failure or the like, and the yield of non-defective semiconductor devices may be significantly reduced.

JP 2000-275820 A JP 2002-343767 A International Publication No. 2006/40956

  The present invention has been made based on the above circumstances, and an object thereof is to provide a pattern forming method capable of suppressing metal elution from a metal-containing film in a multilayer resist process using a metal-containing film. That is.

The invention made to solve the above problems is
(1) forming a metal-containing film on the upper side of the substrate to be processed;
(2) forming a protective film on the metal-containing film,
(3) forming a resist film on the protective film using a resist composition;
(4) a step of exposing the resist film by irradiation of exposure light through a photomask;
(5) A pattern forming method including a step of forming a resist pattern by developing the exposed resist film, and (6) a step of forming a pattern on a substrate to be processed by etching using the resist pattern as a mask. .

  As described above, according to the pattern forming method of the present invention, metal elution from the metal-containing film can be suppressed in the multilayer resist process using the metal-containing film. Therefore, in the pattern formation by the multilayer resist process using the metal-containing film, it is possible to suppress the occurrence of development failure due to the eluted metal and reduce the contamination of the apparatus due to the eluted metal.

<Pattern formation method>
The pattern forming method of the present invention comprises:
(1) forming a metal-containing film on the upper side of the substrate to be processed;
(2) forming a protective film on the metal-containing film,
(3) forming a resist film on the protective film using a resist composition;
(4) a step of exposing the resist film by irradiation of exposure light through a photomask;
(5) a step of forming a resist pattern by developing the exposed resist film; and (6) a step of forming a pattern on a substrate to be processed by etching using the resist pattern as a mask.

  According to the pattern forming method, by providing the step (2), it is considered that the contact between the developer and the metal-containing film can be reduced, and the movement of the eluted metal from the metal-containing film can be suppressed. As a result, metal elution from the metal-containing film can be suppressed. Hereinafter, each process is explained in full detail.

[Step (1)]
In this step, a metal-containing film is formed on the substrate to be processed. “Metal-containing film” refers to a film containing a metal element, and preferably refers to a film having a metal element content of preferably 50% by mass or more, and more preferably 60% by mass or more. Although it does not specifically limit as long as it has the said property as a metal containing film | membrane, For example, a metal film, a metal oxide containing film | membrane, a metal nitride containing film | membrane etc. are mentioned.

  Examples of the substrate to be processed include insulating films such as silicon oxide, silicon nitride, silicon oxynitride, and polysiloxane, and commercially available products such as black diamond (AMAT), silk (Dow Chemical), LKD5109 (JSR), and the like. An interlayer insulating film such as a wafer coated with a low dielectric insulating film. Polysilicon, a so-called metal gate film in which a metal component is injected into polysilicon, and the like are also included. As the substrate to be processed, a patterned substrate such as a wiring course (trench) or a plug groove (via) may be used.

  The method for forming the metal-containing film is not particularly limited, and examples thereof include a method by coating a metal-containing film-forming composition, a method by physical vapor deposition such as a vacuum vapor deposition method, plasma CVD, thermal CVD, atmospheric pressure CVD and the like. Examples thereof include a CVD method, a sputtering method, and a PVD method such as an ion plating method. Among these, since a metal-containing film can be easily formed, a method by applying a metal-containing film-forming composition is preferable.

  Specifically, according to the method of applying the metal-containing film-forming composition, a coating film of this composition is formed by applying the metal-containing film-forming composition to the surface of the substrate to be processed. The metal-containing film can be formed by curing the film by heat treatment, or irradiation with ultraviolet light and heat treatment.

<Metal-containing film forming composition>
The metal-containing film-forming composition is not particularly limited as long as the metal-containing film can be formed, but from the viewpoint of increasing the productivity of the multilayer resist process, more easily forming the metal-containing film,
[A] At least one compound selected from the group consisting of a metal compound having a hydrolyzable group, a hydrolyzate of a metal compound having a hydrolyzable group, and a hydrolysis condensate of a metal compound having a hydrolyzable group (Hereinafter also referred to as “[A] compound”), and [B] a composition containing an organic solvent is preferable. Moreover, this composition can contain [C] water and [D] crosslinking accelerator suitably, and may contain surfactant etc.

[[A] Compound]
The compound [A] is at least one selected from the group consisting of a metal compound having a hydrolyzable group, a hydrolyzate of a metal compound having a hydrolyzable group, and a hydrolysis condensate of a metal compound having a hydrolyzable group. It is this compound.

  [A] The metal species of the compound is not particularly limited as long as it is a metal element, but from the viewpoint of the etching selectivity, the Group 3 element, the Group 4 element, the Group 5 element, the Group 6 element, the Group 12 element are used. At least one metal element selected from the group consisting of group elements and group 13 elements (hereinafter also referred to as “specific elements”) is preferable.

Examples of specific elements include Group 3 elements such as Sc (scandium) and Y (yttrium);
Group 4 elements such as Ti (titanium), Zr (zirconium), Hf (hafnium);
Group 5 elements such as V (vanadium), Nb (niobium), Ta (tantalum);
Group 6 elements such as Cr (chromium), Mo (molybdenum), W (tungsten);
Group 12 elements such as Zn;
Examples include Group 13 elements such as Al (aluminum), Ga (gallium), In (indium), and Tl (thallium).

  Of these specific elements, zirconium, hafnium, tungsten, aluminum, vanadium, and titanium are preferable, and zirconium and tungsten are more preferable.

  Among the compounds [A], the metal compound having a hydrolyzable group is preferably a metal alkoxide, a metal carboxylate, or a metal complex.

(Metal alkoxide)
The said metal alkoxide is a compound which substituted the hydrogen atom of the hydroxyl group which alcohol has with the atom of a metal element, and is represented by following formula (1).

In said formula (1), M is an atom of a metal element. a is an integer of 1 to 7 corresponding to the valence of the atom M. R ¹ is an alkyl group having 1 to 10 carbon atoms which may have an alkoxy group, or a cycloalkyl group having 3 to 10 carbon atoms. However, when R ¹ is plural, a plurality of R ¹ may be the same or different.

  As said alcohol, the compound represented, for example by following formula (2) is preferable.

In said formula (2), R < ² > is synonymous with R < ¹ > in said formula (1).

Examples of the compound represented by the above formula (2) when R ² is an alkyl group or a cycloalkyl group include methanol, ethanol, 1-propanol, 2-propanol, n-butanol, sec-butanol, and pentanol. And cyclohexanol. Examples of the compound represented by the above formula (2) when R ² is an alkyl group substituted with an alkoxy group or a cycloalkyl group include methoxymethanol, methoxyethanol, ethoxymethanol, ethoxyethanol, methoxypropanol, ethoxy Examples include propanol and propoxypropanol.

  Of these, ethanol is more preferred.

(Metal carboxylate)
The said metal carboxylate is a compound which substituted the hydrogen atom of the carboxy group which carboxylic acid has with the atom of the metal element, and is represented by following formula (3).

In said Formula (3), M and a are synonymous with the said Formula (1). R ³ is an organic group. However, if R ³ is plural, the plurality of R ³ may be the same or different.

  As said carboxylic acid, the compound represented, for example by following formula (4) is preferable.

In said formula (4), R < ⁴ > is synonymous with R < ³ > in said formula (3).

  Examples of the compound represented by the above formula (4) include acetic acid, trifluoroacetic acid, 2-methylpropanoic acid, pentanoic acid, 2,2-dimethylpropanoic acid, butanoic acid, hexanoic acid, 2-ethylhexanoic acid, and octane. Examples include acid, nonanoic acid, decanoic acid, acrylic acid, methacrylic acid, and salicylic acid.

(Metal complex)
The metal complex is a compound in which a hydrolyzable group is bonded to an atom of a metal element, and is represented by the following formula (5).

In the above formula (5), M and ^{R 1} is as defined in the above formula (1). R ³ has the same meaning as the above formula (3). b and c are each independently an integer of 0 to 7. However, b + c corresponds to the valence of atom M. d is an integer of 0-7. R ⁵ is an organic compound. However, when R ⁵ is plural, the plurality of R ⁵ may be the same or different.

Examples of the organic compound represented by R ⁵ include ethers represented by the following formula (6).

In said formula (6), R < ⁶ > and R < ⁷ > is a C1-C10 saturated or unsaturated hydrocarbon group which may have an oxygen atom in a frame chain. However, R ⁶ and R ⁷ may be bonded to each other to form a ring structure.

  Examples of the ethers represented by the above formula (6) include methylal, diethyl ether, dipropyl ether, dibutyl ether, diamyl ether, diethyl acetal, dihexyl ether, trioxane, dioxane and the like.

Examples of the organic compound represented by R ⁵ include ketones represented by the following formula (7) or formula (8).

In the above formulas (7) and (8), R ⁸ and R ¹⁰ are each independently a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms which may have a keto group in the skeleton chain. is there. R ⁹ and R ¹¹ are each independently a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms.

  Examples of the ketones represented by the above formula (7) or (8) include acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl cyclohexyl ketone, diethyl ketone, ethyl butyl ketone, trimethylnonanone, Acetonylacetone, mesityl oxide, cyclohexanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), acetylacetone (2,4-pentanedione), 2,4-trifluoropentanedione, 2,4- Hexafluoropentanedione, ethyl acetoacetate, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,3-diphenyl-1,3-propanedione, 1-phenyl-1,3-butanedione, etc. Is mentioned.

Furthermore, examples of the organic compound represented by R ⁵ include esters represented by the following formula (9).

In said formula (9), R < ¹⁴ > is a C1-C10 saturated or unsaturated hydrocarbon group which may have a keto group, a hydroxy group, or an alkoxy group. R ¹⁵ is a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms which may have an alkoxy group.

  Examples of the esters represented by the above formula (9) include ethyl formate, methyl acetate, ethyl acetate, butyl acetate, cyclohexyl acetate, methyl propionate, ethyl butyrate, ethyl oxyisobutyrate, ethyl acetoacetate, ethyl lactate, methoxybutyl. Examples include acetate, diethyl oxalate, and diethyl malonate.

  The hydrolyzate is obtained by hydrolyzing the metal compound having the hydrolyzable group, and the hydrolysis condensate is obtained by further condensing it. This hydrolysis is performed by adding water or water and a catalyst to the metal compound having a hydrolyzable group and stirring at 20 ° C. to 100 ° C. for several hours to several days. As the usage-amount of water, it is 100 mol or less normally with respect to 100 mol of metal compounds which have the said hydrolysable group, Preferably it is 5 mol-50 mol. Examples of the catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; acid catalysts such as organic acids such as acetic acid, propionic acid, butyric acid and maleic acid, sodium hydroxide, potassium hydroxide, ammonia, monoethanolamine, diethanolamine, Examples thereof include inorganic or organic alkali catalysts such as tetramethylammonium hydroxide.

[[B] Organic solvent]
[B] Examples of the organic solvent include alcohol solvents, ketone solvents, amide solvents, ether solvents, ester solvents, and mixed solvents thereof. These solvents can be used alone or in combination of two or more.

Examples of alcohol solvents include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol , Sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec -Monoalcohol solvents such as heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2 -Polyhydric alcohol solvents such as ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, polyhydric alcohol ether solvents such as dipropylene glycol monopropyl ether.

  Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl iso-butyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, and diiso-. Examples include ketone solvents such as butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, and acetophenone.

  Examples of the amide solvents include N, N′-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone and the like can be mentioned.

  Examples of the ester solvents include diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-valerolactone, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, sec-butyl acetate, acetic acid. n-pentyl, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, acetoacetate Ethyl acetate ethylene glycol monomethyl ether, acetate ethylene glycol monoethyl ether, acetate diethylene glycol monomethyl ether, acetate diethylene glycol monoethyl ether, acetate diethylene glycol mono-n-butyl Ether ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriacetate Glycol, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, Examples thereof include dimethyl phthalate and diethyl phthalate.

  Of these [B] organic solvents, propylene glycol monomethyl ether and propylene glycol monoethyl ether are preferred.

  [B] The content of the organic solvent is such that the content of the [A] compound in the metal-containing film-forming composition is 0.5% by mass to 20% by mass, preferably 0.5% by mass in terms of metal oxide. A content of 15% to 15% by mass is preferred.

[[C] water]
The metal-containing film-forming composition preferably further contains [C] water. The metal-containing film-forming composition can further promote the formation reaction of the metal-containing film by further containing [C] water. [C] Water is not particularly limited, and examples thereof include distilled water and ion exchange water. [C] The content of water is preferably 0.1 part by mass to 10 parts by mass, and more preferably 1 part by mass to 8 parts by mass with respect to 100 parts by mass of the metal-containing film forming composition.

[[D] Cross-linking accelerator]
The metal-containing film-forming composition preferably further contains [D] a crosslinking accelerator. [D] A cross-linking accelerator is a compound that generates an acid or a base by light or heat, and the metal-containing film formed when the metal-containing film-forming composition further contains a [D] cross-linking accelerator. The etching selectivity can be improved. [D] Examples of the crosslinking accelerator include onium salt compounds and N-sulfonyloxyimide compounds. [D] The crosslinking accelerator is preferably a thermal crosslinking accelerator that generates an acid or a base by heat, and among these, an onium salt compound is more preferable.

  Examples of the onium salt compounds include sulfonium salts, tetrahydrothiophenium salts, iodonium salts, ammonium salts, and the like.

  Examples of the sulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept- 2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyldiphenylsulfonium perfluoro- n-octanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 2-bicyclo [2.2.1] hept- -Yl-1,1,2,2-tetrafluoroethanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium par Fluoro-n-octanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylphosphonium 1,1, Examples include 2,2-tetrafluoro-6- (1-adamantane carbonyloxy) -hexane-1-sulfonate.

  Examples of the tetrahydrothiophenium salt include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nona. Fluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophene Nitro 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium trifluoromethane Sulfonate, 1- (6-n-butoxynaphthalene-2 Yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (6-n-butoxynaphthalene- 2-yl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) ) Tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydro Thiophenium perfluoro-n-octance Phonates, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, etc. Can be mentioned.

  Examples of the iodonium salt include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl- 1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t -Butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetra Le Oro ethanesulfonate.

  Examples of ammonium salts include ammonium formate, ammonium maleate, ammonium fumarate, ammonium phthalate, ammonium malonate, ammonium succinate, ammonium tartrate, ammonium malate, ammonium lactate, ammonium citrate, ammonium acetate, ammonium propionate, Ammonium butanoate, ammonium pentanoate, ammonium hexanoate, ammonium heptanoate, ammonium octanoate, ammonium nonanoate, ammonium decanoate, ammonium oxalate, ammonium adipate, ammonium sebacate, ammonium butyrate, ammonium oleate, ammonium stearate , Ammonium linoleate, ammonium linolenate, ammonium salicylate, benze Ammonium sulfonate, ammonium benzoate, ammonium p- aminobenzoic acid, ammonium p- toluenesulfonic acid, ammonium methanesulfonate, ammonium trifluoromethanesulfonate, ammonium trifluoroethane sulfonic acid and the like. In addition, the ammonium ion of the above ammonium salt is methylammonium ion, dimethylammonium ion, trimethylammonium ion, tetramethylammonium ion, ethylammonium ion, diethylammonium ion, triethylammonium ion, tetraethylammonium ion, propylammonium ion, dipropylammonium ion Ion, tripropylammonium ion, tetrapropylammonium ion, butylammonium ion, dibutylammonium ion, tributylammonium ion, tetrabutylammonium ion, trimethylethylammonium ion, dimethyldiethylammonium ion, dimethylethylpropylammonium ion, methylethylpropylbutylammonium Ion, triethanolammonium ion, diethanolammonium ion, ammonium salt substituted on the triethanolammonium ions, and the like. Furthermore, 1,8-diazabicyclo [5.4.0] undec-7-ene salt, 1,5-diazabicyclo [4.3.0] -5-nonene salt and the like can be mentioned. As the 1,8-diazabicyclo [5.4.0] undec-7-ene salt, 1,8-diazabicyclo [5.4.0] undec-7-ene formate, 1,8-diazabicyclo [5.4. 0] Undeca-7-ene p-toluenesulfonic acid and the like.

  Examples of the N-sulfonyloxyimide compound include N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy). ) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) bicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide and the like can be mentioned.

  Among these [D] crosslinking accelerators, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) ) Tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydro Thiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, tetraalkylammonium salt, , 8-diazabicyclo [5.4.0] undec-7-ene salt.

  These [D] crosslinking accelerators may be used alone or in combination of two or more. [D] The content of the crosslinking accelerator is preferably 10 parts by mass or less, more preferably 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the [A] compound. [D] By making content of a crosslinking accelerator into the said range, the etching selectivity of the metal containing film | membrane formed can be improved.

[Surfactant]
The surfactant is a component that exhibits an action of improving the coating property, striation, and the like of the metal-containing film forming composition. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol diacrylate. Nonionic surfactants such as stearate are listed. Commercially available surfactants include KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (above, manufactured by Kyoeisha Chemical Co., Ltd.), F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFac F171, F173 (above, manufactured by Dainippon Ink & Chemicals), Fluorad FC430, FC431 ( As above, manufactured by Sumitomo 3M, Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (above, manufactured by Asahi Glass) ) And the like.

  Surfactants may be used alone or in combination of two or more. Moreover, the compounding quantity of surfactant can be suitably determined according to the objective.

  The metal-containing film-forming composition is obtained by dissolving or dispersing the [A] compound and, if necessary, [C] water, [D] a crosslinking accelerator, and other components in the [B] organic solvent at a predetermined ratio. After that, it is usually prepared by filtering with a filter having a pore size of about 0.2 μm.

  Examples of the method for applying the metal-containing film forming composition include a spin coating method, a roll coating method, and a dip method. Moreover, as heating temperature, it is 150 to 500 degreeC normally, Preferably it is 180 to 350 degreeC. The heating time is usually 30 seconds to 1,200 seconds, preferably 45 seconds to 600 seconds. Furthermore, ultraviolet light irradiation may be performed after application of the metal-containing film-forming composition. The thickness of the formed metal-containing film is usually 5 nm to 50 nm.

[Step (2)]
In step (2), a protective film is formed on the metal-containing film. The protective film is usually a non-metallic film. The non-metallic film refers to a film consisting essentially of only a non-metallic element, and preferably refers to a film having a non-metallic element content of preferably 95% by mass or more, more preferably 99% by mass or more. Although it does not specifically limit as a protective film, An organic film and a silicon containing film are preferable. It is considered that when the protective film is the specific film, diffusion of an alkali developer or diffusion of metal from the metal-containing film can be effectively suppressed. As a result, the metal from the metal-containing film can be suppressed. Elution can be further suppressed. Moreover, the pattern shape of the resist pattern formed can be made favorable.

(Organic film)
The organic film is formed by applying an organic film forming composition or the like. The organic film-forming composition contains a polymer, a crosslinking agent, a crosslinking catalyst, an organic solvent, and the like.

(Polymer)
Examples of the polymer include an acrylic resin, a cyclic olefin resin, and a copolymer resin thereof, and among these, an acrylic resin is preferable. Acrylic monomers include compounds that give structural units containing at least one structure selected from the group consisting of lactone structures, cyclic carbonate structures, and sultone structures, compounds that give structural units containing polar groups, and non-acid dissociable compounds Is preferred.

(Crosslinking agent)
Examples of the crosslinking agent include a polyfunctional (meth) acrylate compound, an epoxy compound, a hydroxymethyl group-substituted phenol compound, and a compound having an alkoxyalkylated amino group.

  Examples of the polyfunctional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-butanediol Di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) a Relate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate.

  Examples of the epoxy compound include novolac type epoxy resins, bisphenol type epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins.

  Examples of the hydroxymethyl group-substituted phenol compound include 2-hydroxymethyl-4,6-dimethylphenol, 1,3,5-trihydroxymethylbenzene, 3,5-dihydroxymethyl-4-methoxytoluene [2,6-bis). (Hydroxymethyl) -p-cresol] and the like.

  Examples of the compound having an alkoxyalkylated amino group include hexamethoxymethylated melamine and tetramethoxymethylated glycoluril.

  Among these, tetramethoxymethylated glycoluril is preferable as the crosslinking agent.

(Crosslinking catalyst)
Examples of the crosslinking catalyst include various amine compounds, phenol resins, amino resins, mercaptan compounds, hydrazides, polyphenols, polybasic acids, photoacid generators, thermal acid generators, and the like. Of these, compounds represented by the following formula are preferred.

(Organic solvent)
As an organic solvent, the solvent similar to the solvent illustrated in [B] organic solvent, etc. are mentioned. Of these, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferred.

  Examples of the organic film include films formed from acrylic resins, cyclic olefin resins, copolymer resins, polymer blends, and the like.

  The etching rate of the organic film needs to be higher than that of the resist film from the viewpoint of etching with the resist film. Further, when the processing time is too early, it is not preferable from the viewpoint of process controllability of etching. When paying attention to the carbon content that determines the etching rate, the carbon content of the organic film is preferably 45% by mass or more and less than 70% by mass, and more preferably 50% by mass or more and less than 65% by mass. By setting the carbon content of the organic film within the specific range, a desired resist pattern can be more effectively transferred to the substrate to be processed, and metal elution from the metal-containing film can be further suppressed. .

  The method for forming the organic film is not particularly limited, and examples thereof include a method by coating a composition for forming an organic film containing a polymer and an organic solvent, and a method for melting and coating a polymer. From the viewpoint of being able to form an organic film on the surface and improving the productivity of the multilayer resist process, a method by coating an organic film forming composition is preferred.

(Silicon-containing film)
The silicon-containing film refers to a film containing silicon atoms as main constituent atoms, and the silicon atom content is preferably 20% by mass or more, and more preferably 30% by mass or more.

  Examples of the silicon-containing film include a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a silicon carbide film, and a polycrystalline silicon film.

  The silicon content of the silicon-containing film is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more. By setting the silicon content of the silicon-containing film within the above range, etching selectivity with the resist film can be ensured, and a desired resist pattern can be transferred to the substrate to be processed more effectively.

  As a method for forming a silicon-containing film, for example, a method by application of a composition for forming a silicon-containing film, a method by physical vapor deposition such as vacuum vapor deposition, a method by CVD such as plasma CVD, thermal CVD, atmospheric pressure CVD, or by sputtering And a PVD method such as an ion plating method. Among these, since a silicon-containing film can be easily formed, a method by applying a composition for forming a silicon-containing film is preferable.

  According to the method by application of the silicon-containing film-forming composition, specifically, a coating film of this composition is formed by applying the silicon-containing film-forming composition to the surface of the metal-containing film, A silicon-containing film can be formed by curing the coating film by heat treatment, or irradiation with ultraviolet light and heat treatment.

As the silicon-containing film forming composition,
[A] Polysiloxane [b] A composition containing an organic solvent is preferred. By forming the silicon-containing film using the composition, the silicon-containing film can be more easily formed, and as a result, the productivity of the multilayer resist process can be increased.

[[A] Polysiloxane]
[A] The polysiloxane is not particularly limited as long as it is a polymer having a siloxane bond, but a hydrolysis condensate of a silane compound represented by the following formula (i) is preferable. [A] Silane compounds used for the synthesis of polysiloxane may be used singly or in combination of two or more.

In said formula (i), ^RA is a hydrogen atom, a fluorine atom, a C1-C5 alkyl group, an alkenyl group, an aryl group, or a cyano group. Part or all of the hydrogen atoms of the alkyl group may be substituted with a glycidyloxy group, an oxetanyl group, an acid anhydride group, or a cyano group. Part or all of the hydrogen atoms of the aryl group may be substituted with a hydroxy group. X is a halogen atom or —OR ^B. However, ^{R B} is a monovalent organic group. a is an integer of 0-3. When R ^A and X is plural, respectively, a plurality of R ^A and X may be the same as or different from each other.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^A include:
Linear alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group;
Examples thereof include branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, t-butyl group and isoamyl group.

Examples of the alkenyl group represented by R ^A include a group obtained by removing one hydrogen atom from an alkene compound, and the like. Examples include an ethenyl group, a 1-propen-1-yl group, a 1-propen-2-yl group, 1-propen-3-yl group, 1-buten-1-yl group, 1-buten-2-yl group, 1-buten-3-yl group, 1-buten-4-yl group, 2-butene-1 -Yl group, 2-buten-2-yl group, 1-penten-5-yl group, 2-penten-1-yl group, 2-penten-2-yl group, 1-hexen-6-yl group, 2 -Hexen-1-yl group, 2-hexen-2-yl group, etc. are mentioned. Among these, a group represented by the following formula (i-1) is preferable.

  In said formula (i-1), n is an integer of 0-4. * Indicates a binding site.

N is preferably 0 or 1, and more preferably 0 (in this case, R ^A is a vinyl group).

Examples of the aryl group represented by R ^A include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group.

  Examples of the acid anhydride group that may substitute the alkyl group include a succinic anhydride group, a maleic anhydride group, and a glutaric anhydride group.

  Examples of the alkyl group substituted with the glycidyloxy group include a 2-glycidyloxyethyl group, a 3-glycidyloxypropyl group, and a 4-glycidyloxybutyl group. Among these, a 3-glycidyloxypropyl group is more preferable.

  Examples of the alkyl group substituted with the oxetanyl group include 3-ethyl-3-oxetanylpropyl group, 3-methyl-3-oxetanylpropyl group, 3-ethyl-2-oxetanylpropyl group, 2-oxetanylethyl group and the like. Is mentioned. Of these, a 3-ethyl-3-oxetanylpropyl group is preferred.

  Examples of the alkyl group substituted with the acid anhydride group include a 2-succinic anhydride group-substituted ethyl group, a 3-succinic anhydride group-substituted propyl group, and a 4-succinic anhydride group-substituted butyl group. Among these, a 3-succinic anhydride group-substituted propyl group is more preferable.

  Examples of the alkyl group substituted with the cyano group include a 2-cyanoethyl group, a 3-cyanopropyl group, a 4-cyanobutyl group, and the like.

  Examples of the aryl group substituted with the hydroxy group include a 4-hydroxyphenyl group, a 4-hydroxy-2-methylphenyl group, and a 4-hydroxynaphthyl group. Of these, a 4-hydroxyphenyl group is more preferred.

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

The monovalent organic group represented by R ^B, for example, an alkyl group, an alkylcarbonyl group, and the like. As the alkyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group are preferable. The alkylcarbonyl group is preferably a methylcarbonyl group or an ethylcarbonyl group.

  As said a, the integer of 0-2 is preferable and 1 or 2 is more preferable.

Specific examples of the silane compound represented by the above formula (i) include, for example,
Phenyltrimethoxysilane, benzyltrimethoxysilane, phenethyltrimethoxysilane, 4-methylphenyltrimethoxysilane, 4-ethylphenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane, 4-phenoxyphenyltrimethoxysilane, 4-hydroxy Phenyltrimethoxysilane, 4-aminophenyltrimethoxysilane, 4-dimethylaminophenyltrimethoxysilane, 4-acetylaminophenyltrimethoxysilane, 3-methylphenyltrimethoxysilane, 3-ethylphenyltrimethoxysilane, 3-methoxy Phenyltrimethoxysilane, 3-phenoxyphenyltrimethoxysilane, 3-hydroxyphenyltrimethoxysilane, 3-aminophenyltrimethoxysilane, 3-dimethyl Minophenyltrimethoxysilane, 3-acetylaminophenyltrimethoxysilane, 2-methylphenyltrimethoxysilane, 2-ethylphenyltrimethoxysilane, 2-methoxyphenyltrimethoxysilane, 2-phenoxyphenyltrimethoxysilane, 2-hydroxy Phenyltrimethoxysilane, 2-aminophenyltrimethoxysilane, 2-dimethylaminophenyltrimethoxysilane, 2-acetylaminophenyltrimethoxysilane, 2,4,6-trimethylphenyltrimethoxysilane, 4-methylbenzyltrimethoxysilane 4-ethylbenzyltrimethoxysilane, 4-methoxybenzyltrimethoxysilane, 4-phenoxybenzyltrimethoxysilane, 4-hydroxybenzyltrimethoxysilane, 4-a Roh benzyl trimethoxysilane, 4-dimethylamino-benzyl trimethoxysilane, aromatic ring-containing trialkoxysilane such as 4-acetylamino-benzyl trimethoxysilane;
Methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-t-butoxysilane, methyltriphenoxysilane, Methyltriacetoxysilane, methyltrichlorosilane, methyltriisopropenoxysilane, methyltris (dimethylsiloxy) silane, methyltris (methoxyethoxy) silane, methyltris (methylethylketoxime) silane, methyltris (trimethylsiloxy) silane, methylsilane, ethyltrimethoxysilane Ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxy Silane, ethyltri-sec-butoxysilane, ethyltri-t-butoxysilane, ethyltriphenoxysilane, ethylbistris (trimethylsiloxy) silane, ethyldichlorosilane, ethyltriacetoxysilane, ethyltrichlorosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n-propyl Tri-t-butoxysilane, n-propyltriphenoxysilane, n-propyltriacetoxysilane, n-propyltrichlorosilane, iso-propyltrimethoxysilane, iso-propyltriethoxysilane, is -Propyltri-n-propoxysilane, iso-propyltri-iso-propoxysilane, iso-propyltri-n-butoxysilane, iso-propyltri-sec-butoxysilane, iso-propyltri-t-butoxysilane, iso -Propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri -Sec-butoxysilane, n-butyltri-t-butoxysilane, n-butyltriphenoxysilane, n-butyltrichlorosilane, 2-methylpropyltrimethoxysilane, 2-methylpropyltriethoxysilane, 2-methylpropyltri- n-propoxysilane, 2-methylpropyltri-iso-propoxysilane, 2-methylpropyltri-n-butoxysilane, 2-methylpropyltri-sec-butoxysilane, 2-methylpropyltri-t-butoxysilane, 2 -Methylpropyltriphenoxysilane, 1-methylpropyltrimethoxysilane, 1-methylpropyltriethoxysilane, 1-methylpropyltri-n-propoxysilane, 1-methylpropyltri-iso-propoxysilane, 1-methylpropyltri -N-butoxysilane, 1-methylpropyltri-sec-butoxysilane, 1-methylpropyltri-t-butoxysilane, 1-methylpropyltriphenoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyl Ri-n-propoxysilane, t-butyltri-iso-propoxysilane, t-butyltri-n-butoxysilane, t-butyltri-sec-butoxysilane, t-butyltri-t-butoxysilane, t-butyltriphenoxysilane, alkyltrialkoxysilanes such as t-butyltrichlorosilane and t-butyldichlorosilane;
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltriisopropoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, vinyltri-t-butoxysilane, vinyltriphenoxysilane, allyl Alkenyl such as trimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltriisopropoxysilane, allyltri-n-butoxysilane, allyltri-sec-butoxysilane, allyltri-t-butoxysilane, allyltriphenoxysilane Trialkoxysilanes;
Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-t-butoxysilane;
Tetraarylsilanes such as tetraphenoxysilane;
Epoxy group-containing silanes such as oxetanyltrimethoxysilane, oxiranyltrimethoxysilane, oxiranylmethyltrimethoxysilane, and 3-glycidyloxypropyltrimethoxysilane;
Acids such as 3- (trimethoxysilyl) propyl succinic anhydride, 2- (trimethoxysilyl) ethyl succinic anhydride, 3- (trimethoxysilyl) propyl maleic anhydride, 2- (trimethoxysilyl) ethyl glutaric anhydride Silanes containing anhydride groups;
And tetrahalosilanes such as tetrachlorosilane.

  Of these, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane are preferred from the viewpoint of excellent dry etching resistance of the resulting silicon-containing film, and tetramethoxysilane, phenyltriethoxysilane, and the like. Methoxysilane is more preferred.

In addition to the silane compound represented by the above formula (i), the synthesis of the above [a] polysiloxane includes, for example,
Hexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane, 1,1,1,2,2-pentamethoxy-2-methyldisilane, 1,1,1,2,2-pentaethoxy-2-methyldisilane, 1, 1,1,2,2-pentaphenoxy-2-methyldisilane, 1,1,1,2,2-pentamethoxy-2-ethyldisilane, 1,1,1,2,2-pentaethoxy-2-ethyl Disilane, 1,1,1,2,2-pentaphenoxy-2-ethyldisilane, 1,1,1,2,2-pentamethoxy-2-phenyldisilane, 1,1,1,2,2-pentaethoxy -2-phenyldisilane, 1,1,1,2,2-pentaphenoxy-2-phenyldisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2- Te Laethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraphenoxy-1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-diethyldisilane, 1,1,2, , 2-tetraethoxy-1,2-diethyldisilane, 1,1,2,2-tetraphenoxy-1,2-diethyldisilane, 1,1,2,2-tetramethoxy-1,2-diphenyldisilane, , 1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraphenoxy-1,2-diphenyldisilane,
1,1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,1,2-triphenoxy-1,2,2-trimethyl Disilane, 1,1,2-trimethoxy-1,2,2-triethyldisilane, 1,1,2-triethoxy-1,2,2-triethyldisilane, 1,1,2-triphenoxy-1,2,2 -Triethyldisilane, 1,1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1,2-triethoxy-1,2,2-triphenyldisilane, 1,1,2-triphenoxy-1 1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-dipheno 1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraethyldisilane, 1,2-diethoxy-1,1,2,2-tetraethyldisilane, 1, 2-diphenoxy-1,1,2,2-tetraethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane 1,2-diphenoxy-1,1,2,2-tetraphenyldisilane;
Bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tri-n-propoxysilyl) methane, bis (tri-isopropoxysilyl) methane, bis (tri-n-butoxysilyl) methane, bis ( Tri-sec-butoxysilyl) methane, bis (tri-t-butoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1,2-bis ( Tri-n-propoxysilyl) ethane, 1,2-bis (tri-isopropoxysilyl) ethane, 1,2-bis (tri-n-butoxysilyl) ethane, 1,2-bis (tri-sec-butoxysilyl) ) Ethane, 1,2-bis (tri-t-butoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (di-n-propoxymethylsilyl) -1- (tri-n-propoxysilyl) methane, 1- (di-iso Propoxymethylsilyl) -1- (tri-isopropoxysilyl) methane, 1- (di-n-butoxymethylsilyl) -1- (tri-n-butoxysilyl) methane, 1- (di-sec-butoxymethylsilyl) ) -1- (Tri-sec-butoxysilyl) methane, 1- (di-t-butoxymethylsilyl) -1- (tri-t-butoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (tri Methoxysilyl) ethane, 1- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane, 1- (di-n-propoxymethylsilyl) -2- (tri-n Propoxysilyl) ethane, 1- (di-isopropoxymethylsilyl) -2- (tri-isopropoxysilyl) ethane, 1- (di-n-butoxymethylsilyl) -2- (tri-n-butoxysilyl) ethane 1- (di-sec-butoxymethylsilyl) -2- (tri-sec-butoxysilyl) ethane, 1- (di-t-butoxymethylsilyl) -2- (tri-t-butoxysilyl) ethane,
Bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, bis (di-n-propoxymethylsilyl) methane, bis (di-isopropoxymethylsilyl) methane, bis (di-n-butoxymethylsilyl) Methane, bis (di-sec-butoxymethylsilyl) methane, bis (di-t-butoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (diethoxymethylsilyl) ethane 1,2-bis (di-n-propoxymethylsilyl) ethane, 1,2-bis (di-isopropoxymethylsilyl) ethane, 1,2-bis (di-n-butoxymethylsilyl) ethane, 1, 2-bis (di-sec-butoxymethylsilyl) ethane, 1,2-bis (di-t-butoxymethylsilyl) ethane, (Dimethylmethoxysilyl) methane, bis (dimethylethoxysilyl) methane, bis (dimethyl-n-propoxysilyl) methane, bis (dimethyl-isopropoxysilyl) methane, bis (dimethyl-n-butoxysilyl) methane, bis (dimethyl -Sec-butoxysilyl) methane, bis (dimethyl-t-butoxysilyl) methane, 1,2-bis (dimethylmethoxysilyl) ethane, 1,2-bis (dimethylethoxysilyl) ethane, 1,2-bis (dimethyl) -N-propoxysilyl) ethane, 1,2-bis (dimethyl-isopropoxysilyl) ethane, 1,2-bis (dimethyl-n-butoxysilyl) ethane, 1,2-bis (dimethyl-sec-butoxysilyl) Ethane, 1,2-bis (dimethyl-t-butoxysilyl) ethane,
1- (dimethoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (diethoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (di-n-propoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (di-isopropoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (di-n-butoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (di-sec-butoxymethylsilyl) -1 -(Trimethylsilyl) methane, 1- (di-t-butoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethylsilyl) ethane, 1- (diethoxymethylsilyl) -2 -(Trimethylsilyl) ethane, 1- (di-n-propoxymethylsilyl) -2- (trimethyl Rusilyl) ethane, 1- (di-isopropoxymethylsilyl) -2- (trimethylsilyl) ethane, 1- (di-n-butoxymethylsilyl) -2- (trimethylsilyl) ethane, 1- (di-sec-butoxymethyl) Silyl) -2- (trimethylsilyl) ethane, 1- (di-t-butoxymethylsilyl) -2- (trimethylsilyl) ethane,
1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,2-bis (tri-n-propoxysilyl) benzene, 1,2-bis (tri-isopropoxysilyl) ) Benzene, 1,2-bis (tri-n-butoxysilyl) benzene, 1,2-bis (tri-sec-butoxysilyl) benzene, 1,2-bis (tri-t-butoxysilyl) benzene, 1, 3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,3-bis (tri-n-propoxysilyl) benzene, 1,3-bis (tri-isopropoxysilyl) benzene 1,3-bis (tri-n-butoxysilyl) benzene, 1,3-bis (tri-sec-butoxysilyl) benzene, 1,3-bis (tri-t- Toxisilyl) benzene, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 1,4-bis (tri-n-propoxysilyl) benzene, 1,4-bis (tri -Isopropoxysilyl) benzene, 1,4-bis (tri-n-butoxysilyl) benzene, 1,4-bis (tri-sec-butoxysilyl) benzene, 1,4-bis (tri-t-butoxysilyl) Disilanes such as benzene;
Other silane compounds such as polycarbosilane such as polydimethoxymethylcarbosilane and polydiethoxymethylcarbosilane may be used.

  As content of [a] polysiloxane in the said silicon-containing film formation composition, 80 mass% or more is preferable with respect to the total solid in a silicon-containing film formation composition, 90 mass% or more is more preferable, 95 mass% or more is more preferable. In addition, the said silicon-containing film formation composition may contain 1 type of [a] polysiloxane, and may contain 2 or more types.

  [A] As the molecular weight of polysiloxane, the polystyrene-reduced weight average molecular weight (Mw) by gel permeation chromatography (GPC) is usually 500 to 50,000, preferably 1,000 to 30,000, more preferably. 1,000 to 15,000.

  The thickness of the protective film is preferably 100 nm or less, more preferably 10 nm to 80 nm, and even more preferably 20 nm to 60 nm. By setting the film thickness of the protective film within the above range, a desired resist pattern can be transferred to the substrate to be processed while suppressing metal elution from the metal-containing film more effectively.

[Steps (3) to (5)]
In steps (3) to (5), a resist composition is applied on the protective film, exposed and developed to form a resist pattern. Examples of the resist composition include a positive or negative chemically amplified resist composition containing a photoacid generator, a positive resist composition comprising an alkali-soluble resin and a quinonediazide-based photosensitizer, and an alkali-soluble resin and a cross-link. And negative resist compositions composed of an agent. In the pattern forming method, a commercially available resist composition can also be used as such a resist composition. For example, the resist composition can be applied by a conventional method such as spin coating. In addition, when apply | coating a resist composition, the quantity of the resist composition to apply | coat is adjusted so that the resist film obtained may become a desired film thickness.

  The resist film may be formed by volatilizing a solvent (that is, a solvent contained in the resist composition) in the coating film by pre-baking the coating film formed by applying the resist composition. it can. The pre-baking temperature is appropriately adjusted according to the type of resist composition to be used, but is preferably 30 ° C to 200 ° C, more preferably 50 ° C to 150 ° C. The heating time is usually 30 seconds to 200 seconds, preferably 45 seconds to 120 seconds. In addition, you may provide another coating film on the surface of this resist film. The thickness of the resist film is usually 1 nm to 500 nm, and preferably 10 nm to 300 nm.

Next, the obtained resist film is selectively irradiated with exposure light through a photomask to expose the resist film. As exposure light, depending on the type of acid generator used in the resist composition, electromagnetic waves such as visible light, ultraviolet light, far ultraviolet light, X-rays and γ rays; particles such as electron beams, molecular beams and ion beams Although appropriately selected from the line, far ultraviolet rays are preferable, 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) and extreme ultraviolet light (wavelength 13 nm, etc.) are more preferable. Further, an immersion exposure method can also be employed. The immersion upper layer film may be formed on the resist film using the immersion upper layer film forming composition.

  Post exposure baking (PEB) is preferably performed in order to improve the resolution, pattern profile, developability, and the like of the resist film after exposure. The temperature of the PEB is appropriately adjusted according to the type of resist composition used, but is preferably 180 ° C. or lower, and more preferably 150 ° C. or lower. The heating time is usually 30 seconds to 200 seconds, preferably 45 seconds to 120 seconds.

  After PEB, the resist film is developed to form a resist pattern. The developer used for development can be appropriately selected depending on the type of resist composition used. In the case of a positive chemically amplified resist composition or a positive resist composition containing an alkali-soluble resin, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n- Propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo [5. 4.0] -7-undecene and 1,5-diazabicyclo [4.3.0] -5-nonene. These alkaline aqueous solutions may be those obtained by adding an appropriate amount of a water-soluble organic solvent, for example, alcohols such as methanol and ethanol, and a surfactant.

  Further, in the case of a negative chemically amplified resist composition and a negative resist composition containing an alkali-soluble resin, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, etc. Inorganic alkalis, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine and triethanolamine Alcohol amines, tetramethylammonium hydroxide, tetraethylammonium hydroxide, quaternary ammonium salts such as choline, and alkaline aqueous solutions such as pyrrole, piperidine and other cyclic amines.

[Step (6)]
In this step, a pattern is formed on the substrate to be processed by etching using the resist pattern as a mask. As the etching, one or a plurality of dry etchings are preferably used. When the etching selectivity between the protective film and the resist film is high, the protective film, the metal-containing film, and the substrate to be processed are sequentially dry-etched using the resist pattern as a mask to form a pattern. Dry etching can be performed using a known dry etching apparatus. The source gas during dry etching depends on the elemental composition of the object to be etched, but includes oxygen atoms such as O ₂ , CO, and CO ₂ , inert gases such as He, N ₂ , and Ar, Cl ₂ , chlorine gas such as BCl ₃ , fluorine gas such as CHF ₃ and CF ₄ , gas of H ₂ and NH ₃ , etc. can be used. In addition, these gases can also be mixed and used.

[Step (0)]
The pattern forming method may include a step of forming a resist underlayer film on the substrate to be processed using the resist underlayer film forming composition before the step (1). Thereby, a finer pattern can be formed in the multilayer resist process. As the resist underlayer film forming composition, conventionally known compositions can be used, and examples thereof include NFC HM8005 (manufactured by JSR). As a method for forming the resist underlayer film, for example, a coating film of the resist underlayer film forming composition is formed by coating on a substrate to be processed, and this coating film is subjected to heat treatment, or irradiation with ultraviolet light and heat treatment. For example, curing may be mentioned. Examples of the method for applying the resist underlayer film forming composition include spin coating, roll coating, and dipping. Moreover, as heating temperature, it is 150 to 500 degreeC normally, Preferably it is 180 to 350 degreeC. The heating time is usually 30 seconds to 1,200 seconds, preferably 45 seconds to 600 seconds. The thickness of the resist underlayer film is usually about 50 nm to 500 nm.

In addition, another lower layer film different from the resist lower layer film obtained by using the resist lower layer film forming composition may be formed on the surface of the substrate to be processed. Such another lower layer film may be a carbon film formed by a conventionally known CVD (Chemical Vapor Deposition) method. The other lower layer film is a film provided with an antireflection function, coating film flatness, high etching resistance against a fluorine-based gas such as CF _{4, and the} like. As other lower layer films, for example, commercially available products such as NFC HM8005 (manufactured by JSR) can be used.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

[Preparation of metal-containing film-forming composition]
[Synthesis Example 1]
[A] 7.62 parts by mass of 2,4-pentanedioate tributoxyzirconium (50% by mass butyl acetate / butanol) as a compound, [B] 45.50 parts by mass of propylene glycol monomethyl ether as an organic solvent, and propylene glycol 41.69 parts by mass of monoethyl ether, 5.00 parts by mass of [C] water, and 0.19 parts by mass of [D] diphenyliodonium trifluoromethanesulfonate as a crosslinking accelerator were mixed to form a solution. It filtered with the filter of the hole diameter 0.2micrometer, and prepared the composition (1) for metal containing film formation.

[Synthesis Example 2]
30.00 g of tungsten (V) ethoxide and 60.00 g of propylene glycol monomethyl ether (PGME) were mixed and stirred for 10 minutes at 25 ° C., then mixed with 10.00 g of water, heated to 60 ° C. and heated for 4 hours. Stirring was performed. After completion of the reaction, the reaction mixture was cooled to room temperature, 30.00 g of propylene glycol monomethyl ether was added, and low boiling point substances were removed with an evaporator. It was 10.98 mass% as a result of measuring solid content concentration of a solution by the baking method. [A] 17.34 parts by mass of this solution containing the compound, [B] 46.50 parts by mass of propylene glycol monomethyl ether and 31.06 parts by mass of propylene glycol monoethyl ether as an organic solvent, [C] water 5.00 After mixing 0.10 parts by mass of [D] 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate as a cross-linking accelerator to form a solution, It filtered with the filter of the hole diameter 0.2micrometer, and prepared the composition (2) for metal containing film formation.

[Preparation of composition for forming protective film]
([Α] Synthesis of polymer for organic film)
Polymers (α-1) to (α-3) were synthesized using compounds (M-1) to (M-5) represented by the following formulae.

[Synthesis Example 3] (Synthesis of polymer (α-1))
In a 200 mL flask, 7.00 g (31 mol%) of the compound (M-1), 6.63 g (31 mol%) of the compound (M-3), 6.37 g (38 mol%) of the compound (M-4). Then, 0.55 g of dimethyl 2,2′-azobis (2-methylpropionate) and 40 g of propylene glycol monomethyl ether were charged, and the polymerization reaction was performed by stirring at 80 ° C. for 5 hours under nitrogen.

After completion of the polymerization, the polymerization solution was cooled to 30 ° C. or lower by water cooling, and then poured into a mixed solution of 300 g of methanol: water (mass ratio 9: 1) to precipitate a polymer. After removing the supernatant solution, 60 g of methanol was added to the precipitated polymer to wash the polymer. After removing the supernatant, it was dried at 50 ° C. for 17 hours to obtain a polymer (α-1) (yield 12.8 g, yield 64%). This polymer (α-1) had Mw of 21,600 and Mw / Mn of 2.1. Moreover, as a result of ¹³ C-NMR analysis, the content ratios of structural units derived from (M-1) :( M-3) :( M-4) were 32 mol%: 31 mol%: 37 mol%, respectively. Met.

[Synthesis Example 4] (Synthesis of polymer (α-2))
In a 200 mL flask, 7.00 g (31 mol%) of the compound (M-1), 6.63 g (31 mol%) of the compound (M-3), 6.37 g (38 mol%) of the compound (M-5). , 0.55 g of dimethyl 2,2′-azobis (2-methylpropionate) and 40 g of propylene glycol monomethyl ether were charged and stirred at 80 ° C. for 5 hours under nitrogen. Thereafter, 0.23 g (1 mol%) of dimethyl 2,2′-azobis (2-methylpropionate) was further added, the temperature was raised to 90 ° C., and the mixture was reacted for 1 hour to complete the polymerization.

  After completion of the polymerization, a solution containing the polymer (α-2) was obtained without post-treatment. This polymer (α-2) had Mw of 24,100 and Mw / Mn of 2.2. The solid content concentration of the solution was 33.3% by mass.

[Synthesis Example 5] (Synthesis of polymer (α-3))
A polymer (α-3) was synthesized in the same manner as in Synthesis Example 4 except that the types and amounts of monomers used were as shown in Table 1 below.

  Table 1 also shows the Mw, Mw / Mn, and the content ratio of the structural units derived from the respective monomers of the obtained polymers.

(Preparation of composition for organic film formation)
About each component ([β] cross-linking agent, [γ] cross-linking catalyst, [δ] organic solvent) constituting the composition for forming an organic film other than the synthesized polymers (α-1) to (α-3) Shown in

([Β] cross-linking agent)
Compound represented by the following formula (β-1)

([Γ] cross-linking catalyst)
Compound represented by the following formula (γ-1)

([Δ] solvent)
δ-1: propylene glycol monomethyl ether δ-2: propylene glycol monomethyl ether acetate

[Synthesis Example 6] (Preparation of organic film-forming composition (1))
Polymer (α-1) 100 parts by mass, crosslinking agent (β-1) 20 parts by mass, crosslinking catalyst (γ-1) 5 parts by mass, solvent (δ-1) 1,800 parts by mass and solvent (δ- 2) 1,800 parts by mass were mixed to prepare an organic film forming composition (1).

[Synthesis Examples 7 and 8] (Preparation of organic film-forming compositions (2) and (3))
Organic film-forming compositions (2) and (3) were prepared in the same manner as in Synthesis Example 6 except that the types and amounts of the components used were as described in Table 2 below.

([A] Synthesis of polysiloxane)
[Synthesis Example 9]
1.28 g of oxalic acid was dissolved in 12.85 g of water by heating to prepare an aqueous oxalic acid solution. Thereafter, a cooling tube and a dropping funnel containing the prepared aqueous oxalic acid solution were set in a flask containing 25.05 g of tetramethoxysilane, 3.63 g of phenyltrimethoxysilane, and 57.19 g of propylene glycol monoethyl ether. Subsequently, after heating to 60 degreeC with an oil bath, the oxalic acid aqueous solution was dripped slowly, and it was made to react at 60 degreeC for 4 hours. After completion of the reaction, the flask containing the reaction solution was allowed to cool, and then 50.00 g of propylene glycol monoethyl ether was added, set in an evaporator, and methanol produced by the reaction was distilled off to remove polysiloxane (a-1). 97.3 g of a solution containing was obtained. Solid content concentration in the obtained polysiloxane (a-1) solution was 18.0 mass%. Moreover, Mw of polysiloxane (a-1) was 2,000.

[Synthesis Example 10]
Oxalic acid aqueous solution was prepared by heating and dissolving 1.01 g of oxalic acid in 22.01 g of water. Thereafter, a cooling tube and a dropping funnel containing the oxalic acid aqueous solution prepared above were set in a flask containing 23.93 g of tetramethoxysilane, 21.42 g of methyltrimethoxysilane, and 31.64 g of propylene glycol monoethyl ether. . Subsequently, after heating to 60 degreeC with an oil bath, the oxalic acid aqueous solution was dripped slowly, and it was made to react at 60 degreeC for 4 hours. After completion of the reaction, the flask containing the reaction solution was allowed to cool, and then 50.00 g of propylene glycol monoethyl ether was added and set in an evaporator. Methanol generated by the reaction was distilled off to remove polysiloxane (a-2) A solution containing 98.1 g was obtained. The solid content concentration in the obtained polysiloxane (a-2) solution was 21.5% by mass. Moreover, Mw of polysiloxane (a-2) was 2,700.

(Preparation of silicon-containing film-forming composition)
[B] Organic solvent used for the preparation of the silicon-containing film forming composition is shown below.

([B] Organic solvent)
b-1: Propylene glycol monomethyl ether acetate b-2: Propylene glycol monoethyl ether

[Synthesis Example 11] (Preparation of silicon-containing film-forming composition (1))
The polysiloxane (a-1) solution synthesized in Synthesis Example 9 was dissolved in 100 parts by mass, 3,800 parts by mass of the organic solvent (b-1) and 1,200 parts by mass of the organic solvent (b-2) as a solid content. Then, this solution was filtered with a filter having a pore size of 0.2 μm to obtain a silicon-containing film-forming composition (1).

[Synthesis Example 12]
The polysiloxane (a-2) solution synthesized in Synthesis Example 10 was dissolved in 100 parts by mass, 3,800 parts by mass of the organic solvent (b-1) and 1,200 parts by mass of the organic solvent (b-2) as a solid content. Then, this solution was filtered with a filter having a pore size of 0.2 μm to obtain a silicon-containing film-forming composition (2).

<Pattern formation>
[Example 1]
The metal-containing film-forming composition (1) prepared above is applied onto a silicon wafer as a substrate to be processed by a spin coater and baked on a hot plate at 250 ° C. for 60 seconds to have a diameter of 300 mm and a film thickness of 20 nm. A metal-containing film was formed. On the formed metal-containing film, the organic film-forming composition (1) prepared above was applied by a spin coater and baked at 205 ° C. for 60 seconds to form a protective film which is an organic film having a thickness of 50 nm. On the formed protective film, a resist composition (ARX2014J, manufactured by JSR) was applied and dried at 90 ° C. for 60 seconds to form a resist film having a thickness of 100 nm. A liquid immersion upper layer film-forming composition (NFC TCX091-7, manufactured by JSR) was applied on the formed resist film and dried at 90 ° C. for 60 seconds to form a liquid immersion upper layer film having a film thickness of 30 nm. Thereafter, using an ArF excimer laser exposure apparatus (S610C, manufactured by Nikon Corporation), the substrate was heated at 115 ° C. for 60 seconds after being exposed at an exposure amount of 16 mJ / cm ² by a liquid immersion method. Next, development is performed using an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 30 seconds, and the resist remaining on the silicon wafer and the width of the resulting groove are 50 nm each having a line and space of 50 nm. A resist pattern was formed. In addition, the board | substrate with which the pattern was formed was obtained by dry-etching sequentially using a dry etching apparatus (Telius SCCM, Tokyo Electron) with respect to a metal containing film and a to-be-processed substrate using the formed resist pattern as a mask. .

[Examples 2 to 4]
A resist pattern was formed in the same manner as in Example 1 except that the composition shown in Table 3 below was used as the protective film forming composition, and the firing temperature at the time of forming the protective film was changed to the temperature shown in Table 3. .

[Example 5]
A resist was prepared in the same manner as in Example 1 except that the silicon-containing film-forming composition (2) obtained in Synthesis Example 12 was used as the protective-film-forming composition, and the firing temperature during the formation of the protective film was 220 ° C. A pattern was formed.

[Examples 6 to 10]
Instead of the metal-containing film-forming composition (1), the metal-containing film-forming composition (2) was used, and the protective film-forming composition shown in Table 3 was used. A resist pattern was formed in the same manner as in Example 1 except that it was described in the above.

[Comparative Example 1]
A pattern was formed in the same manner as in Example 1 except that the protective film was not formed.

<Evaluation>
[Metal elution concentration]
A metal-containing film having a diameter of 300 mm and a thickness of 20 nm is formed on a silicon wafer by applying the prepared metal-containing film-forming composition (1) using a spin coater and baking on a hot plate at 250 ° C. for 60 seconds. did. On the formed metal-containing film, each protective film-forming composition shown in Table 3 was applied by a spin coater and baked at the baking temperature shown in Table 3 for 60 seconds to form a protective film having a thickness of 50 nm. An O-ring was placed on the protective film and contacted with the TMAH developer for 3 minutes, and then the TMAH developer was collected. The zirconium or tungsten concentration (metal elution concentration) in the TMAH developer was measured using an ICP-Mass analyzer (7500 cs, manufactured by Agilent), and the amount of metal elution from the metal-containing film was evaluated. The obtained results are shown in Table 3.

[Resist pattern formability]
When the resist pattern formed in each of the above examples and comparative examples is observed with a scanning electron microscope (manufactured by Hitachi High-Technology), the bottom shape of the resist pattern does not become a skirt-spread shape in a 50 nm line and space pattern. The resist pattern formability was evaluated as good (A), and the case where the skirt spread shape was evaluated as defective (B).

  As is apparent from the results in Table 3, according to the pattern forming method of the present invention, by forming a protective film on the metal-containing film, the metal elution into the alkali developer can be compared with the case where no protective film is formed. It was shown that it can be significantly suppressed. Therefore, according to the pattern forming method, in a multi-layer resist process using a metal-containing film, it is possible to suppress the occurrence of development failure due to the eluted metal from the metal-containing film and reduce the contamination of the apparatus due to the eluted metal. It is considered possible.

  The present invention can greatly suppress metal elution from a metal-containing film during development of a resist film in a multilayer resist process using a metal-containing film. Therefore, according to the pattern forming method, it is possible to suppress the occurrence of development failure or the like due to the eluted metal from the metal-containing film and reduce the contamination of the apparatus due to the eluted metal. Therefore, the present invention can be suitably applied in the processing field such as semiconductor device manufacturing where the miniaturization is increasingly advanced.

Claims (4)

(0) A step of forming a resist underlayer film on a substrate to be processed using the resist underlayer film forming composition,
(1) forming a metal-containing film on the resist underlayer film ,
(2) forming a protective film on the metal-containing film,
(3) forming a resist film on the protective film using a resist composition;
(4) a step of exposing the resist film by irradiation of exposure light through a photomask;
(5) the development of the exposed resist film, the step of forming a resist pattern, and (6) by etching with the resist pattern as a mask, to have a process for forming a pattern on a substrate to be processed,
The metal-containing film is
[A] At least one compound selected from the group consisting of a metal compound having a hydrolyzable group, a hydrolyzate of a metal compound having a hydrolyzable group, and a hydrolysis condensate of a metal compound having a hydrolyzable group , And
[B] Organic solvent
Formed using a composition containing
[A] The metal species of the compound is at least one metal selected from the group consisting of Group 3 elements, Group 4 elements, Group 5 elements, Group 6 elements, Group 12 elements and Group 13 elements Element,
A pattern forming method in which the protective film is a silicon-containing film . The silicon-containing film
The pattern forming method according to claim 1 , which is formed using a composition containing [a] polysiloxane and [b] an organic solvent. The pattern formation method according to claim 1 , wherein the silicon-containing film has a silicon content of 20% by mass or more. The pattern forming method according to claim 1 , wherein the protective film has a thickness of 100 nm or less.