JP2010250268A - Stripper liquid for multilayer resist stack and method of processing multilayer resist stack - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resist stripper capable of stripping a resist film and an underlayer film at the same time. <P>SOLUTION: The multilayer resist stack has an inorganic resist underlayer film formed on a substrate directly or through other layers, and a resist film formed on the inorganic resist underlayer film. In the stack, the stripper for the multilayer resist stack is used for removal of the inorganic resist underlayer film and the resist film, and contains (A) quarternary ammonium hydroxide, (B) water-soluble organic solvent, and (C) water. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a stripping solution for multilayer resist laminates and a method for treating multilayer resist laminates.

  In recent years, with the higher integration and higher speed of LSIs, there is a demand for finer pattern rules. In photolithography, which is used as a general-purpose technology, the limit of resolution derived from the wavelength of irradiated light is approaching. It's getting on.

  As a light source for lithography used for forming a resist pattern, g-line (436 nm) or i-line (365 nm) of a mercury lamp has been widely used. Here, as a means for further miniaturizing the resist pattern, a method of shortening the irradiation light wavelength has been effective. A KrF excimer laser (248 nm) or an ArF excimer laser (193 nm) is used as a light source for such irradiation light with a shorter wavelength.

  On the other hand, with the recent rapid miniaturization of pattern rules, the resist film has been made thinner, and this has caused a problem that the resist pattern has poor etching resistance. A multilayer resist process is considered to be effective as a means for solving such problems. As a multilayer resist process, a three-layer resist process is known in which an inorganic resist underlayer film containing silicon atoms is formed between a resist film and an organic resist underlayer film (see Non-Patent Document 1).

  Here, when a laminate is formed on a substrate and the resist film constituting the laminate is patterned, if the resist film is not properly patterned, the resist film is removed and the resist film is removed. It has been studied to form a resist film again on the laminated body.

J. et al. Vac. Sci. Technol. , 16 (6), Nov. / Dec. 1979

  However, in the multilayer resist process, the surface of the inorganic resist underlayer film comes into contact with the developer or the resist stripping solution when the resist film is patterned or the resist film is removed, so that the inorganic resist underlayer film is denatured or roughened. Arise. Therefore, when the resist film is formed again and patterned, the resist film may not be appropriately patterned.

  This invention is made | formed in view of the above subject, and it aims at providing the peeling liquid for multilayer resist laminated bodies which can peel a resist film and an inorganic type resist lower layer film simultaneously.

  When the present inventors used a stripping solution for a multilayer resist laminate containing (A) a quaternary ammonium hydroxide, (B) a water-soluble organic solvent, and (C) water, a resist film and an inorganic resist underlayer The present inventors have found that the film can be peeled off at the same time, and have completed the present invention.

  Specifically, the present invention provides the following.

  A first aspect of the present invention is a multilayer resist comprising an inorganic resist underlayer film formed directly on a substrate or via another layer, and a resist film formed on the inorganic resist underlayer film In the laminate, a stripping solution for a multilayer resist laminate used for removing the inorganic resist underlayer film and the resist film, wherein (A) a quaternary ammonium hydroxide, (B) a water-soluble organic solvent, And (C) a stripping solution for a multilayer resist laminate containing water.

  The second aspect of the present invention includes an inorganic resist underlayer film formed directly on the substrate or via another layer, and a resist film formed on the inorganic resist underlayer film. This is a processing method for a multilayer resist laminate in which the resist film and the inorganic resist underlayer film are removed from the multilayer resist laminate using the multilayer resist laminate release liquid of the present invention.

  According to the stripping solution for a multilayer resist laminate of the present invention, since the resist film and the inorganic resist underlayer film formed under the resist film can be stripped simultaneously, the resist film and the inorganic resist underlayer film that are not properly patterned can be removed. After peeling, an inorganic resist underlayer film and a resist film can be formed again to form a pattern. Moreover, when an inorganic type resist lower layer film is peeled using the multilayer resist laminated body peeling liquid of this invention, it does not affect the process after pattern formation.

  Hereinafter, embodiments of the present invention will be described in detail.

<Stripping solution for multilayer resist laminate>
The stripping solution for multilayer resist laminate of the present invention comprises an inorganic resist underlayer film formed directly on a substrate or via another layer, and a resist film formed on the inorganic resist underlayer film. A stripping solution for a multilayer resist laminate used for removing the inorganic resist underlayer film and the resist film, comprising: (A) a quaternary ammonium hydroxide; and (B) a water-soluble An organic solvent, and (C) water. Furthermore, the multilayer resist stripping solution of the present invention may contain an anticorrosive and an inorganic base.

[(A) Quaternary ammonium hydroxide]
The stripping solution for a multilayer resist laminate of the present invention contains a quaternary ammonium hydroxide. By blending a quaternary ammonium hydroxide, the peelability of the resist film or the inorganic resist underlayer film can be improved.

［上記一般式（１）において、Ｒ^１からＲ^４は、炭素数１から４のアルキル基又はヒドロキシアルキル基である。］ The quaternary ammonium hydroxide is preferably a compound represented by the following general formula (1).

[In the general formula (1), R ¹ to R ⁴ are an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group. ]

  As the quaternary ammonium hydroxide, among the compounds represented by the general formula (1), tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, It is preferable from the point of availability that at least one selected from the group consisting of methyltripropylammonium hydroxide and methyltributylammonium hydroxide is used. Furthermore, tetramethylammonium hydroxide and / or tetraethylammonium hydroxide are particularly preferable from the viewpoint that the solubility of the inorganic resist underlayer film can be improved.

  In the stripping solution for multilayer resist laminate of the present invention, the quaternary ammonium hydroxide is preferably contained in an amount of 0.25% by mass to 20% by mass, and preferably 1% by mass to 15% by mass. Is more preferable. The content of the quaternary ammonium hydroxide is within the above range, so that the resist film and the inorganic resist underlayer film formed under it are kept in good solubility while preventing corrosion to other materials. can do.

[(B) Water-soluble organic solvent]
As the water-soluble organic solvent, compounds commonly used in resist stripping solutions can be used. Water-soluble organic solvents are roughly classified into alkanolamine-based water-soluble organic solvents and other water-soluble organic solvents, and can be appropriately selected and used.

(Alkanolamine water-soluble organic solvent)
Although it does not specifically limit as an alkanolamine type water-soluble organic solvent, Specifically, a monoethanolamine (MEA), a diethanolamine, a triethanolamine, 2- (2-aminoethoxy) ethanol, N, N- Dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine , And triisopropanolamine. These compounds may be used alone or in combination of two or more.

  Among the above-mentioned compounds, monoethanolamine, 2- (2-aminoethoxy) ethanol, and N-methylethanolamine are preferable as the alkanolamine-based water-soluble organic solvent.

(Water-soluble organic solvents other than alkanolamine-based water-soluble organic solvents)
The water-soluble organic solvent other than the alkanolamine-based water-soluble organic solvent is not particularly limited. Specifically, sulfoxides such as dimethyl sulfoxide; dimethyl sulfone, diethyl sulfone, bis (2-hydroxyethyl) sulfone And sulfones such as tetramethylenesulfone; amides such as N, N-dimethylformamide, N-methylformamide, N, N-dimethylacetamide, N-methylacetamide, and N, N-diethylacetamide; N-methyl- Lactams such as 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, and N-hydroxyethyl-2-pyrrolidone; β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and Lactones such as ε-caprolactone; imidazolidinones such as 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, and 1,3-diisopropyl-2-imidazolidinone ; And ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene Recall monomethyl ether, and dipropylene glycol monomethyl ether, glycerin, 1,2-butylene glycol, 1,3-butylene glycol, and polyhydric alcohols such as 2,3-butylene glycol, and derivatives thereof. These compounds may be used alone or in combination of two or more.

  Among the above compounds, water-soluble organic solvents other than alkanolamine-based water-soluble organic solvents include dimethyl sulfoxide, dimethylimidazolidinone, N-methyl-2-pyrrolidone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. Is preferred.

  As the water-soluble organic solvent, any of alkanolamine-based water-soluble organic solvents and other water-soluble organic solvents may be used, but when any of them is used alone, other than alkanolamine-based water-soluble organic solvents It is preferable to use a water-soluble organic solvent. In this case, the corrosion of materials other than the resist film and the inorganic resist lower layer film can be further suppressed as compared with the case where the alkanolamine water-soluble organic solvent is used.

  As the water-soluble organic solvent, an alkanolamine-based water-soluble organic solvent and other water-soluble organic solvents may be used as a mixed solvent. By using such a mixed solvent, the solubility of the resist film can be further improved.

(Water-soluble organic solvent content)
In the stripping solution for multilayer resist laminate of the present invention, the water-soluble organic solvent is preferably contained in an amount of 20% by mass or more and 99% by mass or less, and more preferably 40% by mass or more and 80% by mass or less. When the content of the water-soluble organic solvent is within the above range, the solubility of the resist film and the inorganic resist underlayer film formed under the resist film is kept good, and corrosion to other materials is prevented. Can do.

  When a mixed solvent of an alkanolamine-based water-soluble organic solvent and other water-soluble organic solvents is used as the water-soluble organic solvent, the alkanolamine-based water-soluble organic solvent is used with respect to the total amount of the multilayer resist stripping solution. The content is preferably 5% by mass or more and 70% by mass or less, and more preferably 10% by mass or more and 50% by mass or less.

[(C) Water]
The stripping solution for a multilayer resist laminate of the present invention contains water. The water content is preferably 0.75% by mass to 60% by mass, and more preferably 3% by mass to 45% by mass. When the water content is within the above range, corrosion of other materials can be prevented while maintaining good solubility of the resist film and the inorganic resist underlayer film formed under the resist film.

[(D) Anticorrosive]
The stripping solution for a multilayer resist laminate of the present invention may contain an anticorrosive agent as necessary. As an anticorrosive agent, at least 1 sort (s) chosen from a benzotriazole type compound and a mercapto group containing compound can be used.

(Benzotriazole compounds)
Examples of the benzotriazole compounds include benzotriazole compounds represented by the following general formula (2).

［上記一般式（２）において、Ｒ^５及びＲ^６は、それぞれ独立に水素原子、置換基を有していてもよい炭素数１から１０の炭化水素基、カルボキシル基、アミノ基、水酸基、シアノ基、ホルミル基、スルホニルアルキル基、又はスルホ基であり、Ｑは水素原子、水酸基、置換基を有していてもよい炭素原子数１から１４の炭化水素基（ただし、当該炭化水素基はアミド結合、又はエステル結合で中断されていてもよい）、又は下記一般式（３）で表される基である。］

[In the general formula (2), R ⁵ and R ⁶ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, a carboxyl group, an amino group, a hydroxyl group, cyano. Group, a formyl group, a sulfonylalkyl group, or a sulfo group, and Q is a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 14 carbon atoms that may have a substituent (provided that the hydrocarbon group is an amide) Or may be interrupted by a bond or an ester bond), or a group represented by the following general formula (3). ]

［上記一般式（３）において、Ｒ^７は炭素数１から６のアルキレン鎖であり、Ｒ^８及びＲ^９は、それぞれ独立に、水素原子、水酸基、又は炭素数１から６のヒドロキシアルキル基若しくはアルコキシアルキル基である。］

[In the general formula (3), R ⁷ is an alkylene chain having 1 to 6 carbon atoms, and R ⁸ and R ⁹ are each independently a hydrogen atom, a hydroxyl group, or a hydroxyalkyl group having 1 to 6 carbon atoms, An alkoxyalkyl group; ]

In the above general formula (2), in each definition of R ⁵ , R ⁶ and Q, the hydrocarbon group may be either an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and has an unsaturated bond. Further, it may be linear, branched, or cyclic. Examples of the aromatic hydrocarbon group include a phenyl group and a p-tolyl group. Examples of the linear aliphatic hydrocarbon group include a methyl group, an n-propyl group, and a vinyl group. Examples of the branched aliphatic hydrocarbon group include an i-butyl group and a t-butyl group. Examples of the cyclic aliphatic hydrocarbon group include a cyclopentyl group and a cyclohexyl group. Examples of the hydrocarbon group having a substituent include a hydroxyalkyl group and an alkoxyalkyl group.

In the general formula (2), Q is preferably a group represented by the general formula (3). In particular, among the groups represented by the general formula (3), it is preferable to select a group in which R ⁸ and R ⁹ are each independently a hydroxyalkyl group or alkoxyalkyl group having 1 to 6 carbon atoms.

  Furthermore, it is also preferable that Q is selected so that the compound represented by the general formula (2) exhibits water solubility. Specifically, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (that is, a methyl group, an ethyl group, a propyl group, and an isopropyl group), a hydroxyalkyl group having 1 to 3 carbon atoms, a hydroxyl group, and the like are preferable.

  Specific examples of the benzotriazole compounds include benzotriazole, 5,6-dimethylbenzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-aminobenzotriazole, 1-phenylbenzotriazole, 1-phenylbenzotriazole, Hydroxymethylbenzotriazole, methyl 1-benzotriazolecarboxylate, 5-benzotriazolecarboxylic acid, 1-methoxy-benzotriazole, 1- (2,2-dihydroxyethyl) -benzotriazole, and 1- (2,3-dihydroxy Propyl) benzotriazole; and 2,2 ′-{[(4-methyl-1H-benzotriazol-1-yl) methyl] imino, commercially available from Ciba Specialty Chemicals as the “IRGAMET” series Bisethanol, 2,2 ′-{[(5-methyl-1H-benzotriazol-1-yl) methyl] imino} bisethanol, 2,2 ′-{[(4-methyl-1H-benzotriazole-1- Yl) methyl] imino} bisethane, 2,2 ′-{[(4-methyl-1H-benzotriazol-1-yl) methyl] imino} bispropane, and the like. Among these, 1- (2,3-dihydroxypropyl) -benzotriazole, 2,2 ′-{[(4-methyl-1H-benzotriazol-1-yl) methyl] imino} bisethanol, and 2,2 '-{[(5-Methyl-1H-benzotriazol-1-yl) methyl] imino} bisethanol and the like are preferably used. These benzotriazole compounds may be used alone or in combination of two or more.

(Mercapto group-containing compound)
As the mercapto group-containing compound, a compound having a hydroxyl group and / or a carboxyl group in at least one of the α-position and β-position of the carbon atom bonded to the mercapto group is preferable. Specific examples of such compounds include 1-thioglycerol, 3- (2-aminophenylthio) -2-hydroxypropyl mercaptan, 3- (2-hydroxyethylthio) -2-hydroxypropyl mercaptan, and 2-mercapto. Examples include propionic acid and 3-mercaptopropionic acid. Among the above compounds, it is particularly preferable to use 1-thioglycerol.

(Content of anticorrosive)
The content of the anticorrosive agent in the stripping solution for multilayer resist laminate of the present invention is preferably 0.05% by mass or more and 10% by mass or less, and more preferably 0.1% by mass or more and 1% by mass or less. preferable. When the content of the anticorrosive is within the above range, corrosion of the metal material constituting the wiring layer can be effectively prevented.

[(E) Inorganic base]
The stripping solution for a multilayer resist laminate of the present invention can contain an inorganic base as necessary. By including an inorganic base in the stripping solution for a multilayer resist laminate, the stripping property of the inorganic resist underlayer film can be particularly improved.

  The inorganic base that can be added to the stripping solution for a multilayer resist laminate of the present invention is not particularly limited, but lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. It is preferable to use an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide.

(Inorganic base content)
When the inorganic base is contained in the stripping solution for multilayer resist laminate of the present invention, the content is preferably 0.1 mmol / L or more and 200 mmol / L or less. When the content of the inorganic base is within the above range, the resist film and the inorganic resist underlayer film formed under it are satisfactorily damaged without damaging the metal material constituting the wiring layer. Can be dissolved. The content is more preferably 1 mmol / L or more and 20 mmol / L or less.

[PH]
In the present invention, when 100 ml of the stripping solution for multilayer resist laminate temperature-controlled at 25 ° C. is measured for 1 minute with a pH meter calibrated with standard solutions of pH 4 and pH 7, The pH is preferably 10 or more. When the pH is 10 or more, the solubility of the resist film and the inorganic resist underlayer film formed under the resist film can be increased. The pH is more preferably 11 or more, and still more preferably 12 or more.

[Method for preparing stripping solution for multilayer resist laminate]
In the present invention, the stripping solution for multilayer resist laminate is obtained by diluting, for example, a solution (concentrated solution) containing a high concentration of each component in the stripping solution for multilayer resist laminate with a solvent such as water or a water-soluble organic solvent. Can be prepared. That is, the concentrate for preparing the multilayer resist laminate release liquid is appropriately prepared in consideration of the composition of the multilayer resist laminate release liquid, the solvent used for dilution, the dilution ratio, and the like. . Here, also about the concentrate for preparing stripping solution for multilayer resist laminated bodies, (A) quaternary ammonium hydroxide, (B) water-soluble organic solvent, and the dilution liquid for multilayer resist laminated bodies, (C) It contains water and belongs to the scope of the present invention. In addition, it is preferable to perform dilution of the said concentrate with only water. By using the concentrated liquid as described above, costs for transportation and the like can be reduced.

<Multilayer resist laminate>
The multilayer resist laminate to which the stripping solution for multilayer resist laminate of the present invention is applied is not particularly limited as long as it is a multilayer resist laminate having an inorganic resist underlayer film and a resist film. However, the multilayer resist laminate is provided with a resist film, an inorganic resist underlayer film containing silicon atoms, and an organic resist underlayer film provided under the inorganic resist underlayer film. It is preferable that it is a 3 layer resist laminated body which has.

[Organic resist underlayer film]
As a material for forming the organic resist underlayer film, a material used for forming the resist underlayer film in the two-layer resist laminate and the three-layer resist laminate can be widely used. The material for forming the resist underlayer film is a hydrocarbon compound that can be etched with oxygen gas, and a compound that can provide the resist underlayer film with sufficient etching resistance as a mask when the substrate underneath is etched. Is preferred.

［上記一般式（４）において、Ｒ^ｓ１は、水素原子、ヒドロキシル基、アルキル基、アリール基、又はヒドロキシル基、ポリエーテル基、カルボニル基、エステル基、ラクトン基、アミド基、エーテル基、及びニトリル基からなる群から選ばれる少なくとも１種の官能基を有する１価の有機基を表し、複数のＲ^ｓ１は、互いに異なっていてもよい。ａは０以上２以下の整数である。］ [Inorganic resist underlayer film]
The inorganic resist underlayer film can be formed using a known inorganic resist underlayer film forming composition. In particular, the inorganic resist underlayer film that can be suitably peeled off using the stripping solution for multilayer resist laminates of the present invention is an inorganic film containing silicon, and as a composition for forming a silicon-based inorganic resist underlayer film Various silicon-containing polymers can be used. Although the said silicon containing polymer will not be specifically limited if it is the material conventionally used as a material of the composition for inorganic type resist underlayer film formation, A siloxane polymer can be mentioned. Examples of the siloxane polymer include a polymer having a structural unit represented by the following general formula (4).

[In the general formula (4), R ^s1 represents a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, or a hydroxyl group, a polyether group, a carbonyl group, an ester group, a lactone group, an amide group, an ether group, and a nitrile. It represents a monovalent organic group having at least one functional group selected from the group consisting of groups, and the plurality of R ^s1 may be different from each other. a is an integer of 0 or more and 2 or less. ]

  The plurality of structural units represented by the general formula (4) of the siloxane polymer may be different from each other.

In the case where the siloxane polymer is a siloxane polymer represented by the general formula (4) and having a structural unit in which R ^s1 is an organic group, and the molecular weight ratio of the organic component to the molecular weight of the siloxane polymer is high. When the stripping solution for multilayer resist laminate of the present invention contains an inorganic base, the solubility of the inorganic resist underlayer film in the stripping solution for multilayer resist laminate tends to be improved. Therefore, the siloxane polymer is a siloxane polymer represented by the general formula (4) and having a structural unit in which R ^s1 is an organic group, and the molecular weight ratio of the organic component to the molecular weight of the siloxane polymer is 50%. When occupying the above, it is preferable that the stripping solution for multilayer resist laminate contains an inorganic base.

In particular, in the case of a siloxane polymer having many constituent units in which R ^s1 is a bulky aryl group such as a phenyl group, the multilayer resist lamination stripping solution preferably contains an inorganic base.

［上記一般式（５）において、Ｒ^ｓ１及びａは上記と同様であり、Ｒ^ｓ２は炭素数１以上５以下のアルコキシ基又はハロゲン原子を示し、複数のＲ^ｓ２は、互いに異なっていてもよい。］ The siloxane polymer can be obtained by condensation polymerization of a monomer represented by the following general formula (5).

[In the general formula (5), R ^s1 and a are the same as above, R ^s2 represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom, and a plurality of R ^s2 may be different from each other. . ]

  The composition for forming an inorganic resist underlayer film includes the siloxane polymer, a solvent, and, if necessary, a surfactant and an acid generator.

[Resist film]
A conventionally known photoresist composition can be used as a material for forming the resist film. The photoresist composition may be a negative photoresist composition, a positive photoresist composition, a chemically amplified photoresist composition, or any other photoresist composition. It may be. However, an extremely high-precision pattern can be obtained by forming a resist film using a chemically amplified photoresist composition.

  In the present invention, it is particularly preferable to use an organic resist film as the resist film. As this organic resist film, the base polymer does not contain an inorganic component such as silicon.

  The stripping solution for a multilayer resist laminate of the present invention is applied when the resist film is not appropriately patterned in the multilayer resist laminate. That is, a part of the surface of the inorganic resist underlayer film is denatured by the developing solution for developing the exposed resist film, so even if the resist film is formed again on the inorganic resist underlayer film, In this process, patterning may not be performed properly. For this reason, using the stripping solution for multilayer resist laminate of the present invention, the resist film that has not been properly patterned and the inorganic resist underlayer film are removed, and then the inorganic resist underlayer film and the resist film are again removed. A good resist pattern can be obtained by forming.

<Processing method for multilayer resist laminate>
The processing method for a multilayer resist laminate of the present invention includes an inorganic resist underlayer film formed directly on a substrate or via another layer, and a resist film formed on the inorganic resist underlayer film. This is a processing method for a multilayer resist laminate in which the resist film and the inorganic resist underlayer film are removed from the multilayer resist laminate using the stripping solution for multilayer resist laminate of the present invention.

  The processing method of the multilayer resist laminate is performed when the resist film that forms the multilayer resist laminate is patterned and the resist film is not properly patterned. This is performed to remove the resist film and the inorganic resist underlayer film from the laminate.

  In the method for treating a multilayer resist laminate of the present invention, the multilayer resist laminate to which this is applied is preferably a three-layer resist laminate. That is, as described above, the multilayer resist laminate is preferably composed of an organic resist underlayer film, an inorganic resist underlayer film, and a resist film.

  In the method for treating a multilayer resist laminate of the present invention, the method for bringing the multilayer resist laminate and the multilayer resist laminate stripping solution into contact with each other is not particularly limited, and a commonly performed method can be adopted. it can. Specifically, for example, a dipping method, a paddle method, a shower method, or the like can be used to bring the multilayer resist laminate into contact with the stripping solution for the multilayer resist laminate.

  Hereinafter, the present invention will be described in detail with reference to examples. Note that the present invention is not limited to the following examples.

ＴＭＡＨ：テトラメチルアンモニウム水酸化物
ＤＭＳＯ：ジメチルスルホキシド
ＰＧＭＥ：プロピレングリコールモノメチルエーテル
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
ＥＤＧ：ジエチレングリコールモノエチルエーテル
ＭＤＧ：ジエチレングリコールモノメチルエーテル <Examples 1 to 5, Comparative Examples 1 to 5>
Based on the composition shown in Table 1 below, a release solution for a multilayer resist laminate was prepared, and the peelability of the resist film and the peelability of the inorganic resist underlayer film were evaluated. In addition, the reagent which is generally marketed was used about the reagent which does not have description in particular about an acquisition source among each reagent. Moreover, the numerical value in a table | surface is represented by the unit of the mass% unless there is particular notice.

TMAH: Tetramethylammonium hydroxide DMSO: Dimethyl sulfoxide PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate EDG: Diethylene glycol monoethyl ether MDG: Diethylene glycol monomethyl ether

<Evaluation>
[Removability of resist film]
A resist film-forming composition was applied to a silicon wafer, pre-baked at 90 ° C. for 90 seconds, and then post-baked at 180 ° C. for 90 seconds to form a 450 nm-thick resist film. This resist film was immersed at 25 ° C. in the stripping solutions for multilayer resist laminates of Examples and Comparative Examples, and the presence or absence of the resist film after 15 minutes was evaluated according to the following criteria. The results are shown in Table 1.
◎: Completely peeled ○: Almost peeled ×: Could not be peeled

  In addition, as said resist film formation composition, the following components are melt | dissolved in the mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) / ethyl lactate (EL) = 60/40, and solid content concentration is 6.3 mass%. What was adjusted to was used.

Resin: Resin having a unit represented by the following chemical formulas (C1), (C2), and (C3) at a ratio of C1: C2: C3 = 50: 30: 20 (molar ratio) (molecular weight 10,000): 100 mass Part Acid generator: Compound represented by the following chemical formula (A1): 13 parts by mass Acid quencher: Tri-n-pentylamine: 0.54 parts by mass Additive: γ-butyrolactone ... 10 Parts by mass
Salicylic acid: 1.32 parts by mass
XR104 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) ... 0.10 parts by mass

[Peelability of inorganic resist underlayer]
An organic resist underlayer film forming material was applied to a 20 cm silicon wafer and heated at 250 ° C. for 90 seconds to form an organic resist underlayer film having a thickness of 300 nm.

  The organic resist underlayer film forming material is a copolymer having a molar ratio of a constituent unit derived from 1-adamantyl methacrylate and a constituent unit derived from p-hydroxystyrene in a molar ratio of 60:40. (Mw = 6000) 100 parts by mass, glycoluril-based crosslinking agent (product name: Nicalac MX270, manufactured by Sanwa Chemical Co., Ltd.), 20 parts by mass, surfactant (product name: XR104, manufactured by Dainippon Ink & Chemicals, Inc.) 0.05 1.0 part by mass of an additive (product name: Catalyst 602, manufactured by Nippon Cytec Co., Ltd.) is dissolved in a mixed solvent of PGMEA / EL = 6/4 so that the solid content concentration becomes 14.3% by mass. What was adjusted to was used.

  Next, an inorganic resist underlayer film forming composition was applied onto the organic resist underlayer film, and heated at 250 ° C. for 90 seconds to form an inorganic resist underlayer film having a thickness of 140 nm.

  The composition for forming an inorganic resist underlayer film is 50 parts by mass of the following resin A (mass average molecular weight: 9700), 50 parts by mass of resin B (mass average molecular weight: 720), and 0.3 mass of hexadecyltrimethylammonium acetate. Part, 0.75 part by mass of malonic acid was added to a mixed solvent of PGMEA / EL = 6/4, and the polymer solid content concentration of the resin A and the resin B was adjusted to 2.5% by mass. Things were used.

Resin A

Resin B

  The numerical value added to the lower right of the constituent unit of each resin indicates the abundance ratio (molar ratio) of each constituent unit.

The laminate of the organic resist underlayer film and the inorganic resist underlayer film is immersed in the release liquid for multilayer resist laminates of Examples and Comparative Examples at 25 ° C. for 1 minute, and the inorganic resist after immersion according to the following criteria The presence or absence of the lower layer film was evaluated. The results are shown in Table 1.
◎: Completely peeled ○: Almost peeled ×: Could not be peeled

[Peelability of multilayer resist laminate]
An organic resist underlayer film having a film thickness of 300 nm was formed on a 20 cm silicon wafer by the same method as that used in the evaluation of [Releasability of inorganic resist underlayer film], and the film thickness was changed to 50 nm thereon. An inorganic resist underlayer film was formed by the same method as that used in the evaluation of [Removability of inorganic resist underlayer film] to prepare a laminate. Furthermore, a resist film was formed on the laminate by the same method as that used in the evaluation of [Removability of resist film] except that the film thickness was 120 nm, and a multilayer resist laminate was prepared. The multilayer resist laminate was immersed in a release solution for multilayer resist laminates of Examples and Comparative Examples at 25 ° C. for 3 minutes, and the presence or absence of the multilayer resist laminate after immersion was evaluated according to the following criteria. The results are shown in Table 1.
◎: Completely peeled ○: Almost peeled ×: Could not be peeled

  From Table 1, it can be seen that the stripping solution for multilayer resist laminate of the present invention can satisfactorily strip both the resist film and the inorganic resist underlayer film. On the other hand, the stripping solution for multilayer resist laminate of the comparative example had good solubility in either the resist film or the inorganic resist underlayer film, but could not peel both well.

ＴＭＡＨ：テトラメチルアンモニウム水酸化物
ＴＥＡＨ：テトラエチルアンモニウム水酸化物
ＤＭＳＯ：ジメチルスルホキシド <Examples 6 to 10>
Based on the composition shown in Table 2 below, the composition described in Example 1 was added to 100 ppm (about 1.8 mmol / L) to 500 ppm (about 8.9 mmol / L) potassium hydroxide, 500 ppm (about 12.5 mmol / L). L) sodium hydroxide was added to evaluate the peelability of the inorganic resist underlayer film. For potassium hydroxide and sodium hydroxide, commercially available reagents were used. Moreover, the numerical value in a table | surface shall be represented by the unit of the mass% unless there is particular notice.

TMAH: Tetramethylammonium hydroxide TEAH: Tetraethylammonium hydroxide DMSO: Dimethyl sulfoxide

<Evaluation>
[Peelability of inorganic resist underlayer]
An organic resist underlayer film forming material was applied to a 20 cm silicon wafer and heated at 250 ° C. for 90 seconds to form an organic resist underlayer film having a thickness of 300 nm.

  The organic resist underlayer film forming material is a copolymer having a molar ratio of a constituent unit derived from 1-adamantyl methacrylate and a constituent unit derived from p-hydroxystyrene in a molar ratio of 60:40. (Mw = 6000) 100 parts by mass, glycoluril-based crosslinking agent (product name: Nicalac MX270, manufactured by Sanwa Chemical Co., Ltd.), 20 parts by mass, surfactant (product name: XR104, manufactured by Dainippon Ink & Chemicals, Inc.) 0.05 1.0 part by mass of an additive (product name: Catalyst 602, manufactured by Nippon Cytec Co., Ltd.) is dissolved in a mixed solvent of PGMEA / EL = 6/4 so that the solid content concentration becomes 14.3% by mass. What was adjusted to was used.

  Next, the inorganic resist underlayer film forming composition is spin coated on the organic resist underlayer film at 500 rpm for 1 second, then at 1000 rpm for 30 seconds, heated at 100 ° C. for 1 minute, and then at 400 ° C. for 30 minutes, An inorganic resist underlayer film having a thickness of 140 nm was formed.

  In addition, the composition for forming an inorganic resist underlayer film includes 100 parts by mass of the following resin C (mass average molecular weight: 9400), 0.3 parts by mass of hexadecyltrimethylammonium acetate, and 0.75 parts by mass of malonic acid, PGMEA / The mixture was added to a mixed solvent of EL = 6/4 and adjusted so that the polymer solid content concentration of Resin C was 2.5% by mass.

Resin C

  The numerical value added to the lower right of the constituent unit of each resin indicates the abundance ratio (molar ratio) of each constituent unit.

The laminate of the organic resist underlayer film and the inorganic resist underlayer film is immersed in the stripping solution for multilayer resist laminates of Example 1 and Examples 6 to 10 at 25 ° C. for 1 to 5 minutes, and the following criteria The presence or absence of an inorganic resist underlayer film after immersion was evaluated. The results are shown in Table 2.
○: The film was completely removed ×: The film residue was confirmed

  From the above, it was found that the inorganic resist underlayer film can be more satisfactorily removed by adding an inorganic base to the stripping solution for multilayer resist laminates of the present invention.

Claims (9)

An inorganic resist underlayer film formed directly on the substrate or via another layer;
A multilayer resist laminate having a resist film formed on the inorganic resist underlayer film, wherein the inorganic resist underlayer film and the resist film are used for removing the resist film. ,
(A) Stripping solution for multilayer resist laminate comprising quaternary ammonium hydroxide, (B) water-soluble organic solvent, and (C) water.   The stripping solution for a multilayer resist laminate according to claim 1, comprising (A) quaternary ammonium hydroxide in an amount of 0.1% by mass to 20% by mass. The stripping solution for a multilayer resist laminate according to claim 1 or 2, wherein the (A) quaternary ammonium hydroxide is a compound represented by the following general formula (1).

In above general formula (1), ^{R 4} a ^{R 1} is an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms. ]   The (A) quaternary ammonium hydroxide is tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltripropylammonium hydroxide, and methyltributyl. The stripping solution for a multilayer resist laminate according to any one of claims 1 to 3, which is at least one selected from the group consisting of ammonium hydroxides.   The stripping solution for a multilayer resist laminate according to any one of claims 1 to 4, further comprising (D) an anticorrosive.   The stripping solution for a multilayer resist laminate according to any one of claims 1 to 5, further comprising (E) an inorganic base.   The stripping solution for a multilayer resist laminate according to any one of claims 1 to 6, wherein the pH of the stripping solution for the multilayer resist laminate is 10 or more.   The stripping solution for a multilayer resist laminate according to claim 1, wherein the inorganic resist underlayer film is made of a siloxane polymer.   A multilayer resist laminate having an inorganic resist underlayer film formed directly on a substrate or via another layer and a resist film formed on the inorganic resist underlayer film, The processing method of the multilayer resist laminated body which removes the said resist film and the said inorganic type resist underlayer film using the peeling liquid for multilayer resist laminated bodies as described in any one of.