TW201106117A - Stripping liquid used in multiple photoresist layer incorporation and processing method of same - Google Patents

Abstract

The present invention provides a photoresist stripping liquid which can simultaneously strip the photoresist film and become the coating film of its lower layer. The present invention provides a stripping liquid used in multiple photoresist layer, which is used to form directly or through the other layer the inorganic photoresist lower-layer film on the substrate and to form the multiple photoresist layer incorporation of the photoresist film on the aforementioned inorganic photoresist lower-layer film. The aforementioned inorganic photoresist lower-layer film and the aforementioned photoresist film is removed by using the stripping liquid used in multiple photoresist layer incorporation, which contains (A) the quaternary ammonium hydroxide, (B) the water-soluble organic solvent, and (C) the water.

Description

201106117 VI. Description of the Invention: [Technical Field] The present invention relates to a peeling liquid for a multilayer photoresist laminate and a method for treating a multilayer photoresist layer. [Prior Art] In recent years, with the high integration and high speed of LSI, in the demand for pattern size miniaturization, photolithography used as a general-purpose technique has approached the resolution limit derived from the wavelength of illumination light. . A light source for lithography used in the formation of a photoresist pattern is widely used as a g-line (4 3 6 n m ) or an i-line (3 6 5 n m ) of a mercury lamp. Among them, a method of making the photoresist pattern more fine makes the irradiation light shorter wavelength effective. The source of the short-wavelength illumination light is a KrF excimer laser (248 nm) or an ArF excimer laser (193 nm). On the other hand, in recent years, as the pattern standard has been miniaturized, the photoresist film has been thinned, which causes a problem that the etching resistance of the photoresist pattern is lowered. As a method of solving such problems, a multilayer photoresist process is effective. As for the multilayer photoresist process, a three-layer photoresist process in which an inorganic photoresist underlayer film containing germanium atoms is formed between a photoresist film and an organic photoresist underlayer film is known (see Non-Patent Document 1). Here, in the case where a laminate is formed on a substrate and the photoresist film constituting the laminate is patterned, the photoresist film is removed and the photoresist film is removed. A photoresist film is again formed on the laminate. -5-201106117 [Prior Art Document] [Non-Patent Document] [Non-Patent Document 1] JL Vac. Sci. Technol., 16(6), Nov./Dec. 19 7 9 [Summary of the Invention] [Inventive To Solve Problem] However, in the multilayer photoresist process, when the pattern of the photoresist film or the removal of the photoresist film is removed, the surface of the underlying film of the inorganic photoresist is in contact with the developing solution or the photoresist stripping liquid, so that the inorganic light is made. The underlayer film is modified or cracked. Therefore, &gt; the photoresist film is formed again, and when the pattern is formed, the photoresist film cannot be properly patterned. The present invention has been made in view of the above problems, and an object thereof is to provide a peeling liquid for a multilayer photoresist layer which can simultaneously peel off a photoresist film and an inorganic photoresist underlayer film. [Means for Solving the Problem] The present inventors have found that when a peeling liquid for a multilayer photoresist layer comprising (A) quaternary ammonium hydroxide, (B) a water-soluble organic solvent, and (C) water is used, The photoresist film and the inorganic photoresist underlayer film are simultaneously peeled off, and thus the present invention has been completed. Specifically, the present invention provides the following. The first aspect of the present invention is a stripping liquid for a multilayer photoresist laminate for use in an underlying film of inorganic -6-201106117 having a direct or transparent layer formed on a substrate and the inorganic light. a multilayer photoresist layer for blocking a photoresist film formed on the underlayer film, and a stripping liquid for a multilayer photoresist layer for removing the inorganic photoresist underlayer film and the photoresist film, which is characterized by containing (A) quaternary ammonium a hydroxide, (B) a water-soluble organic solvent, and (C) water. Further, a second aspect of the present invention is a method for treating a multilayer photoresist laminate which comprises using the stripping liquid for a multilayer photoresist laminate of the present invention, and an inorganic system having a layer formed directly on the substrate or through another layer. The multilayer photoresist layer of the photoresist underlayer film and the photoresist film formed on the inorganic photoresist underlayer film removes the photoresist film and the inorganic photoresist underlayer film. [Effect of the Invention] According to the peeling liquid for a multilayer photoresist laminate of the present invention, since the photoresist film and the inorganic photoresist underlayer film formed on the lower layer can be simultaneously peeled off, the photoresist film which cannot be appropriately patterned can be used. After the inorganic photoresist underlayer film is peeled off, an inorganic photoresist lower layer mold is again formed. The photoresist film forms a pattern. Further, when the inorganic photoresist underlayer film is peeled off by using the multilayer photoresist laminate peeling liquid of the present invention, it does not affect the step after pattern formation. [Embodiment] Hereinafter, embodiments of the present invention will be described in detail. <Release for Multilayer Photoresist Laminate> The peeling liquid for multilayer photo pi laminate of the present invention is used for an inorganic photoresist underlayer film formed directly or through other layers on a substrate and the above-mentioned 201106117 inorganic photoresist a multilayer photoresist layer of a photoresist film formed on the underlayer film, which removes the above-mentioned inorganic photoresist lower layer film and the multilayer photoresist layer peeling liquid for the photoresist film, which contains (A) quaternary ammonium hydroxide (B) a water-soluble organic solvent and (C) water. Further, the multilayer photoresist release liquid of the present invention may further contain an anticorrosive agent or an inorganic base. [(A) Quaternary Ammonium Hydroxide] The peeling liquid for a multilayer photoresist laminate of the present invention contains a quaternary ammonium hydroxide. By disposing the quaternary ammonium hydroxide, the peeling property of the photoresist film and the inorganic photoresist underlayer film can be improved. The above quaternary ammonium hydroxide is preferably a compound represented by the following formula (1). [NR 1 R2R3R4] +ΟΗ~ · - (1) [In the above formula (1), R1 to R4 are an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group]. As the quaternary ammonium hydroxide, the compound represented by the above formula (1) is preferably selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrahydric hydroxide. At least one of the group consisting of propylammonium, tetrabutylammonium hydroxide, methyltripropylammonium hydroxide, and methyltributylammonium hydroxide. Further, from the viewpoint of improving the solubility of the inorganic photoresist underlayer film, tetramethylammonium hydroxide and/or tetraethylammonium hydroxide are preferable. The peeling liquid for a multilayer photoresist laminate of the present invention preferably contains 0.25 mass% or more and 20 mass% or less of a quaternary ammonium hydroxide, more preferably 1 -8 to 201106117 mass% or more and 15 mass% or less. By setting the content of the quaternary ammonium hydroxide in the above range, on the one hand, the solubility of the photoresist film or the inorganic photoresist underlayer film formed on the lower layer can be favorably maintained, and on the other hand, it can prevent the other materials. corrosion. [(B) Water-Soluble Organic Solvent] 'The water-soluble organic solvent can be a compound conventionally used in a photoresist stripper. The water-soluble organic solvent is roughly classified into an alkanolamine-based water-soluble organic solvent and other water-soluble organic solvents, and can be appropriately selected and used. (Alkanolamine-based water-soluble organic solvent) The alkanolamine-based water-soluble organic solvent is not particularly limited, and specific examples thereof include monoethanolamine (MEA), diethanolamine, triethanolamine, and 2-(2-amino group B. Oxy)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 singly or in combination of two or more. The alkanolamine-based water-soluble organic solvent is preferably a monoethanolamine, 2-(2-aminoethoxy)ethanol or N-methylethanolamine in the above compound. (Water-soluble organic solvent other than the alkanolamine-based water-soluble organic solvent) The water-soluble organic solvent other than the alkanolamine-based water-soluble organic solvent is not particularly limited, and specifically, it is an anthracene such as dimethyl hydrazine; Dimethyl-9- 201106117 Anthraquinone, diethylaluminum, bis(2-hydroxyethyl)anthracene and tetramethylene maple; N,N-dimethylformamide, N-methyl Indoleamines such as decylamine, N,N-dimethylacetamide, N-methylacetamide and N,N-diethylacetamide; N-methyl-2-pyrrolidone, N -Ethyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, and N-transethylethyl-2·pyrrolidone and other internal amines; , 7-butyrolactone, 7-valerolactone ' &lt; 5- valerolactone 'caprolactone, and lactones such as ε-caprolactone; 1,3-dimethyl-2-imidazolidinone, Imidazolidinone such as ι,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, Ethylene glycol, diethylene glycol monoacetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, two Polyols such as propylene glycol monomethyl ether, glycerin, 1,2-butanediol, 1,3-butanediol, and 2,3-butanediol, and derivatives thereof. These compounds may be used singly or in combination of two or more. The water-soluble organic solvent other than the alkanolamine-based water-soluble organic solvent, and among the above compounds, preferred are dimethyl hydrazine, dimethyl imidazolidinone, fluorene-methyl-2-pyrrolidone, and diethylene glycol. Monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether. As the water-soluble organic solvent, any one of an alkanolamine-based water-soluble organic solvent and a water-soluble organic solvent other than the above may be used. However, when either one is used alone, it is preferred to use a water-soluble organic solvent other than the alkanolamine-based water-soluble organic solvent. Organic solvents. In this case, corrosion of a material other than the photoresist film or the inorganic photoresist underlayer film -10-201106117 can be further suppressed as compared with the case of using an alkanolamine-based water-soluble organic solvent. Further, as the water-soluble organic solvent, a mixed solvent of an alkanolamine-based water-soluble organic solvent and a water-soluble organic solvent other than the above may be used. The solubility of the photoresist film can be further improved by using these mixed solvents. (Content of Water-Soluble Organic Solvent) The release liquid for a multilayer photoresist laminate of the present invention preferably contains 20% by mass or more and 99% by mass or less of a water-soluble organic solvent, more preferably 40% by mass or more, and 8 0% by mass or less. By setting the content of the water-soluble organic solvent within the above range, on the one hand, the solubility of the photoresist film or the inorganic photoresist underlayer film formed on the lower layer can be favorably maintained, and on the one hand, corrosion of other materials can be prevented. Further, when a mixed solvent of an alkanolamine-based water-soluble organic solvent and a water-soluble organic solvent other than the solvent is used as the water-soluble organic solvent, the 'alkanolamine-based water-soluble organic solvent preferably contains 5 with respect to the total amount of the multilayer resist stripper. The mass% or more and 7 mass% or less are more preferably 1% by mass or more and 50% by mass or less. [(C) Water] The peeling liquid for a multilayer photoresist laminate of the present invention contains water. The content of water is preferably 0.75% by mass or more and 60% by mass or less, more preferably 3% by mass or more and 45% by mass or less. By making the water content within the above range, the solubility of the photoresist film or the inorganic photoresist underlayer film formed on the lower layer can be favorably maintained, and corrosion of other materials can be prevented. -11 - 201106117 [(D) Anticorrosive Agent] The peeling liquid for a multilayer photoresist laminate of the present invention may contain an anticorrosive agent as needed. As the anticorrosive agent, at least one selected from the group consisting of a benzotriazole-based compound and a compound containing a mercapto group can be used. (Benzotriazole-based compound) The benzotriazole-based compound is a benzotriazole-based compound represented by the following formula (2). [Chemical 2]

[In the above formula (2), R5 and R6 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, a carboxyl group, an amine group, a hydroxyl group, a cyano 'mercapto group, a sulfoalkyl group Or a sulfo group, Q is a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 14 carbon atoms which may have a substituent (wherein the hydrocarbon group may also be interrupted by a hydrazine bond or an ester bond), or represented by the following formula (3) Base]. [化3]

[In the above formula (3), R7 is an alkylene chain having a carbon number of 1 to 6 'R8 and R9 are each independently a hydrogen atom, a hydroxyl group, or a hydroxyalkyl group or alkoxyalkyl group having 1 to 6 carbon atoms] . Further, in the above formula (2), in the definitions of R5, R6 and Q, the 'hydrocarbon-12-201106117 group may be any of an aromatic hydrocarbon group or an aliphatic hydrocarbon group' may have an unsaturated bond, or may be Any of a linear chain, a branched chain, or a ring. The aromatic hydrocarbon group may, for example, be a phenyl group, a p-tolyl group or the like. The linear aliphatic hydrocarbon group may, for example, be a methyl group, a n-propyl group or a vinyl group. The branched aliphatic hydrocarbon group may, for example, be an isobutyl group, a tert-butyl group or the like. The cyclic aliphatic hydrocarbon group may, for example, be a cyclopentyl group or a cyclohexyl group. The hydrocarbon group having a substituent may, for example, be a hydroxyalkyl group or an alkoxyalkyl group. Further, in the above formula (2), Q is preferably a group represented by the above formula (3). In particular, it is preferred that R8 and R9 in the group represented by the above formula (3) are each independently selected from the group of a hydroxyalkyl group or an alkoxyalkyl group having 1 to 6 carbon atoms. The compound represented by the above formula (2) shows a water-soluble one. Specifically, it is preferably a hydrogen atom, a group having 1 to 3 carbon atoms (i.e., 'methyl group, ethyl group, propyl group and isopropyl group), a hydroxyalkyl group having 1 to 3 carbon atoms, and a hydroxyl group. Specific examples of the benzotriazole-based compound include, for example, benzotriazole, 5,6-dimethylbenzotriazole, hydrazine-hydroxybenzotriazole, hydrazine-methylbenzotriazole, and 1-amine. Benzotriazole, 1-phenylbenzotriazole, hydroxymethylbenzotriazine, methyl 1-benzotriazolecarboxylate, 5-benzotriazolecarboxylic acid, 丨-methoxy- Benzotriazine, 1-(2,2·dihydroxyethyl)-benzotriazole and dihydroxypropyl)benzotriazole; and 2,2' sold by the "IRGAMENT" series of gasoline and petrol chemicals -{[(4-methyl-1H-benzotriazin-1-yl)methyl]imino}diethanol, 2,2,-{[(5-methyl-1H-benzotriazole- 1-yl)methyl]imino}diethanol, 2,2,-{[(4-methyl-1H-benzotriazol-1-yl)-13- 201106117 methyl]imido} double Ethane and 2,2'-{[(4-methyl-1H-benzotriazole)methyl]imino} bispropane. It is preferred to use 1-(2,3-propylpropyl)-benzotriazole, 2,2'-{[(4-methyl-1^benzotriazole)methyl]imido]} Ethanol and 2,2'-{[(5-methyl-111-benzotriyl)methyl]imino}}diethanol. These benzotriazole compounds may be used singly or in combination of two or more. (The compound containing a mercapto group) The compound containing a mercapto group is preferably a compound such as a compound having a hydroxyl group and/or a carboxyl group bonded to at least one of the carbon 11 11-position and the 0-position of the mercapto group. Thioglycerol, 3-(2-Phenylthio)-2-hydroxypropylthiol, 3-(2-hydroxyethylthio)propylthiol, 2-mercaptopropionic acid, and 3-mercaptopropionic acid and the like. It is preferred to use 1-thioglycerol in the above sections. (The content of the anticorrosive agent) The content of the anti-waste in the peeling liquid for a multilayer photoresist laminate of the present invention is preferably 0.05% by mass or more and 10% by mass or less, more preferably 100% by mass or more and 1% by mass or less. By making the content of the anticorrosive agent in the right range, corrosion of the metal material constituting the wiring layer can be effectively prevented. [(Ε) Inorganic Base] The peeling liquid for a multilayer photoresist laminate of the present invention can be used as a base. The inorganic 1-cyano-dihydroxy-buxazole-1-isotope is contained in the stripping solution for the multilayer photoresist layer. The base benzene-2-hydroxyl etchant is 0 · 1 : the above-mentioned sister η /», , , especially -14-201106117, which makes the peeling property of the inorganic photoresist underlayer film good. The inorganic base to be added to the peeling liquid for a multilayer photoresist laminate of the present invention is not particularly limited, but an alkali metal hydrogen such as lithium hydroxide, sodium hydroxide, potassium hydroxide, hydrogenated ruthenium or oxyhydrin is preferably used. Oxide, better use of sodium hydroxide and potassium hydroxide. (Content of Inorganic Base) When the inorganic liquid is contained in the stripping liquid for the multilayer photoresist layer of the present invention, the content thereof is preferably l.1 mmol/L or more and 200 mmol/L or less. When the content of the inorganic base is within the above range, corrosion of the metal material or the like constituting the wiring layer is not caused, and the photoresist film and the inorganic photoresist underlayer film formed on the lower layer can be satisfactorily dissolved. The above content is more preferably 1 mmol/L or more and 20 mmol/L or less. [pH] In the present invention, when the stripping liquid for a multilayer photoresist layer adjusted to a temperature of 25 ° C is measured by a pH meter adjusted to a standard solution of pH 4 and pH 7 for 100 ml-minute, the stripping liquid for the multilayer photoresist layer is used. The pH is preferably 10 or more. By setting the pH to 10 or more, the solubility of the photoresist film under the photoresist film and the underlying layer of the organic film can be improved. The above pH is preferably 11 or more, and more preferably 12 or more. [Preparation Method of Stripping Liquid for Multilayer Photoresist Laminate] In the present invention, the stripping liquid for a multilayer photoresist laminate can be diluted with a solvent such as water or water -15-201106117 a soluble organic solvent to contain a high concentration of, for example, a multilayer resist. The laminate is prepared by using a solution (concentrate) of each component in the stripping solution. In other words, the concentrated liquid for preparing the peeling liquid for a multilayer photoresist laminate is considered to be suitable for preparation of a peeling liquid for a multilayer photoresist laminate, a solvent for dilution, and a dilution ratio. In addition, the concentrated liquid for modulating the multilayer light-receiving liquid is also the same as the diluent for the multilayer photoresist laminate, and contains (A) a quaternary ammonium hydroxide, (B) a water-soluble organic solvent, and C) Water, and is within the scope of this application. Further, the dilution of the above concentrate is preferably carried out only with water. The concentrate such as the above can reduce the cost of transportation and the like. <Multilayered photoresist layer> The multilayer photoresist layer to which the release liquid for a multilayer photoresist layer of the present invention is applied is not particularly limited as long as it is a multilayer photoresist layer having an inorganic photoresist underlayer film and a photoresist film. However, the multilayer photoresist layer is preferably a photoresist film, an inorganic photoresist underlayer film containing germanium atoms disposed on the lower layer of the photoresist film, and an organic layer disposed on the lower layer of the inorganic photoresist underlayer film. A three-layer photoresist laminate of a photoresist underlayer film. [Organic Photoresist Underlayer Film] As a material for forming an organic photoresist underlayer film, a two-layer photoresist layer and a three-layer photoresist layer can be widely used for forming a photoresist underlayer film. The material for forming the photoresist underlayer film is a hydrocarbon compound which can be etched by oxygen, and it is also preferable to use a compound which imparts sufficient etching resistance to the underlayer film as a mask for etching the underlying substrate. [Inorganic Photoresist Underlayer Film] The inorganic photoresist underlayer film can be formed using a conventional inorganic resist underlayer film forming composition. In particular, the inorganic resist underlayer film which is suitably peeled off by the stripping liquid for a multilayered photoresist layer of the present invention is an inorganic film containing ruthenium, and various inorganic thin resist film forming compositions can be used as the lanthanum-based inorganic resist underlayer film forming composition. a polymer containing ruthenium. The ruthenium-containing polymer is not particularly limited as long as it is a material used as a material for forming an inorganic photoresist underlayer film, but a siloxane polymer is exemplified. The siloxane polymer may, for example, be a polymer having a constituent unit represented by the following formula (4):

[In the above formula (4), Rsl represents a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, or has a group selected from the group consisting of a hydroxyl group, a polyether group, a carbonyl group, an ester group, a lactone group, a decyl group, an ether group, and a nitrile group. One of the at least one functional group of the group is valence organic, and the plurality of Rs1 may be different from each other; a is an integer of 0 or more and 2 or less]. The plurality of constituent units represented by the above formula (4) which the above-mentioned siloxane polymer has may be different from each other. Further, the above-mentioned siloxane polymer is a siloxane polymer having a constituent unit of Rsl represented by the above formula (4) as an organic group, and the molecular weight ratio of the organic component in the molecular weight of the siloxane polymer When the height is high, -17-201106117 The peeling liquid for a multilayer photoresist laminate of the present invention tends to improve the solubility of the inorganic photoresist underlayer film to the peeling liquid for a multilayer photoresist laminate by containing an inorganic base. According to the above, the above-mentioned siloxane polymer is a siloxane polymer having a structural unit of Rs1 represented by the above formula (4) as an organic group, and the organic component of the molecular weight of the above siloxane polymer When the molecular weight ratio accounts for 50% or more, the peeling liquid for a multilayer photoresist laminate preferably contains an inorganic test. In particular, in the case of a decane polymer having a plurality of constituent units of a high volume aryl group such as a phenyl group, the stripping solution for a multilayer photoresist layer preferably contains an inorganic base. The above siloxane polymer can be obtained by polycondensation of a monomer represented by the following formula (5). (R, 1) . -S i -R·2 (4_β) (5) [In the above formula (5), RS1 and a are the same as described above, and Rs2 represents a carbon number of 1 or more. 5 or less of an alkoxy group or a halogen atom, and the plural Rs 2 may be different from each other]. The inorganic photoresist underlayer film forming composition contains the above-described decane polymer, a solvent, and optionally a surfactant and an acid generator. [Photoresist Film] As the material for forming the photoresist film, a conventional photoresist composition can be used. The photoresist composition may be a negative photoresist composition, a positive photoresist composition, a chemically amplified photoresist composition, or a photoresist composition other than the photoresist composition. However, by forming a photoresist film using a chemically amplified photoresist composition, a pattern with an extremely high accuracy of -18 - 201106117 can be obtained. Further, in the present invention, it is preferred to use an organic photoresist film as the photoresist film. The organic photoresist film does not contain an inorganic component such as ruthenium in the base polymer. The peeling liquid for a multilayer photoresist laminate of the present invention is suitable for use in a case where the photoresist film cannot be appropriately patterned in the above multilayer photoresist laminate. That is, since one part of the surface of the inorganic photoresist underlayer film is modified by the developing liquid for developing the exposed photoresist film, even if the inorganic photoresist is formed on the upper layer of the underlying film, the photoresist is formed again. The film is not properly patterned in the subsequent steps. According to this, the photoresist film for the multilayer photoresist layer of the present invention can be used to remove the photoresist film and the inorganic photoresist underlayer film which are not properly patterned, and then, by further forming the inorganic photoresist underlayer film and the photoresist film. , and a good photoresist pattern can be obtained. <Processing Method of Multilayer Photoresist Layer> The multilayer method of the present invention is a method for treating a photoresist layer using the stripping liquid for a multilayer photoresist layer of the present invention, which has an inorganic system formed directly on the substrate or through other layers. A multilayer photoresist layer of a photoresist underlayer film and a photoresist film formed on the underlayer film of the inorganic photoresist, and a method of treating the multilayer photoresist layer of the photoresist film and the inorganic photoresist underlayer film. The method for treating the multilayer photoresist layer is carried out in a case where the photoresist film constituting the multilayer photoresist layer is patterned, and the photoresist film cannot be appropriately patterned, and is used. The photoresist film and the inorganic photoresist underlayer film are removed from the multilayer photoresist layer which is not properly patterned. In the method for treating a multilayer photoresist layer of the present invention, the multilayer photoresist layer to which the method is applied -19-201106117 is preferably a three-layer photoresist laminate. That is, the above-mentioned 'multilayer photoresist layer is preferably composed of an organic photoresist underlayer film, an inorganic photoresist underlayer film, and a photoresist film. In the method for treating a multilayer photoresist layer of the present invention, the method of bringing the multilayer photoresist laminate into contact with the stripping liquid for a multilayer photoresist laminate is not particularly limited, and a usual method can be employed. Specifically, for example, a method in which a multilayer photoresist layer is brought into contact with a peeling liquid for a multilayer photoresist laminate by using a dipping method, a paddle stirring method, and a shower method is exemplified. [Examples] Hereinafter, examples of the invention will be described in detail. Further, the present invention is not limited to the embodiments listed below. <Examples 1 to 5, Comparative Examples 1 to 5 &gt; The composition shown in Table 1 below was used to prepare a peeling liquid for a multilayer photoresist laminate, and the peeling property of the photoresist film and the underlying film of the inorganic photoresist were evaluated. Peelability. Further, if the source obtained in each of the reagents is not specifically described, a commercially available reagent is used. Further, the number in the table is expressed in units of mass ° / 〇 unless otherwise specified. -20- 201106117 [Table 1]

(8) Tetra-ammonium hydroxide (Β) Water-soluble organic solvent (C) Peelability of peeling multilayer photoresist layer of peeling inorganic photoresist underlayer film of water other photoresist film Example 1 12 (12.5 DMSO (δϋ) (37. 5) - ◎ ◎ ◎ Example 2 ΤΜΑΗ (0.25) DMSO (99) {0. 75) - ◎ © ◎ Example 3 ΤΜΑΗ (20) DMSO (20) (60) - Ο ◎ © Example 4 ΤΜΑΗ (12.5) EDG (50) (37. S) - ◎ ◎ ◎ Example 5 ΤΜΑΗ (12.5) MDG (50) (37. 5) - ◎ ◎ ◎ Comparative Example 1 ΤΜΑΗ (25) - (75) - X ◎ X Comparative Example 2 - - - PGME/PGMEA (70/30) ◎ XX Comparative Example 3 - DMSO (100) - - ◎ XX Comparative Example 4 ΤΜΑΗ (22. 5) DMSO ( 10) (67. 5) - X ◎ X Comparative Example 5 ΤΜΛΗ (〇·1) DMSO (15) (84. 9) - XXX ΤΜΑΗ : tetramethylammonium hydroxide DMSO: dimethyl hydrazine PGME: propylene glycol single Methyl ether PGMEA : propylene glycol monomethyl ether acetate-21 - 201106117 EDG : diethylene glycol monoethyl ether MDG : diethylene glycol monomethyl ether <Evaluation> [Removal of photoresist film] Yu Yu Coating a photoresist film on the wafer The composition was prebaked at 90 ° C for 90 seconds, and then baked at 180 ° C for 90 seconds to form a photoresist film having a film thickness of 450 nm. The photoresist film was immersed in a peeling liquid for a multilayer photoresist laminate of Examples and Comparative Examples at 25 ° C, and the presence or absence of the photoresist film was evaluated after 15 minutes on the following basis. The results are shown in Table 1. ◎: completely peeled off: substantially peeled off X: not peelable and 'the above-mentioned composition for forming a photoresist film was used to dissolve the following components in propylene glycol monomethyl ether acetate (PGMEA) / ethyl lactate (EL) = 60 In the mixed solvent of /40, it was adjusted to a solid concentration of 6.3% by mass. Resin: a resin having a unit represented by the following chemical formulas (C1), (C2), and (C3) with a mass ratio of 100 parts by weight: 100 parts by weight: C2: C3 = 50:30:20 (mole ratio) 100 parts by mass of an acid generator : a compound represented by the following chemical formula (A1): 13 parts by mass of an acid deactivator: tri-n-pentylamine...0.54 parts by mass of an additive: r-butyrolactone... 10 parts by mass - 22 201100117 Salicylic acid ... 1.3 2 mass XR104 (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.) ... 〇.1〇质量份 [化6]

(C1) (C2) (C3)

[Inorganic Photoresist Underlayer Film Peeling Property] An organic photoresist underlayer film forming material was applied onto a wafer of 20 cm, and heated at 250 ° C for 90 seconds to form an organic photoresist underlayer film having a film thickness of 300 nm. Further, the material for forming an organic photoresist lower layer film is a molar ratio of 100 parts by mass of a constituent unit derived from 1-adamantyl methacrylate to a constituent unit derived from p-hydroxystyrene. a copolymer of 60:4 ( (M w = 690 ), 20 parts by mass of a diol urea-based crosslinking agent (product name: NIKALAC MX270 'manufactured by Sanwa Chemical Co., Ltd.), 〇. 〇 5 parts by mass Surfactant (product name: XR 1 04 'Daily Ink 23-201106117 manufactured by Chemical Co., Ltd.), 1.0 part by mass of additive (product name: Catalyst 602, manufactured by Nippon Science and Technology Co., Ltd.) dissolved in PGMEA/EL = 6/ The solid content concentration was adjusted to 14.3% by mass in the mixed solvent of 4. Then, an inorganic resist underlayer film forming composition was applied onto the organic photoresist underlayer film, and heated at 250 ° C for 90 seconds to form an inorganic resist underlayer film having a film thickness of 140 nm. Further, the composition for forming an inorganic resist underlayer film is a resin A (mass average molecular weight: 9700) of 50 parts by mass or less, a resin B (mass average molecular weight: 720) of 50 parts by mass, and acetic acid of 0.3 parts by mass. Cetyltrimethylammonium, 〇.75 parts by mass of malonic acid Addition D in a mixed solvent of PGMEA/EL = 6/4, the concentration of the polymer solid component of the resin A and the resin B is adjusted to 2.5% by mass. Resin A [Chemical 7]

Resin B [Chemical 8]

Si〇3/2 CH3

(B) -24- 201106117 The constituents of each resin in the lower right note indicate the proportion of each constituent unit (Morby ratio). The laminate of the organic photoresist underlayer film and the inorganic photoresist underlayer film was immersed in the peeling liquid for a multilayer photoresist laminate of the examples and the comparative examples at 25 ° C for 1 minute, and the inorganic after the immersion was evaluated by the following criteria. Whether the photoresist is under the film. The results are not in Table 1. ◎: completely peeled off: substantially peeled off X: peeling off [peelability of multilayer photoresist laminate] was carried out on a 20 cm wafer on the evaluation of [exfoliation of inorganic photoresist underlayer film] In the same manner as in the method of forming an organic photoresist underlayer film having a film thickness of 300 nm, except that the film thickness on the film is 50 nm, the method is the same as that in the evaluation of the [peelability of the inorganic photoresist underlayer film]. Method An inorganic photoresist underlayer film was formed to form a laminate. Further, on the laminate, a photoresist film was formed in the same manner as in the evaluation of [peelability of the photoresist film] except that the film thickness was 12 Å, and a multilayer photoresist layer was produced. The multilayer photoresist layer was laminated to 25. (: immersed in the peeling liquid for multilayer photoresist layers of the examples and the comparative examples for 3 minutes, and the presence or absence of the multilayer photoresist layer after immersion was evaluated by the following criteria. The results are shown in Table 1. ◎: Complete peeling 〇: approximate Upper peeling X: Unpeelable peeling -25-201106117 It can be understood from Table 1 that the peeling liquid for a multilayer photoresist laminate of the present invention can peel off both the photoresist film and the inorganic photoresist underlayer film well. In contrast, the comparative example The peeling liquid for a multilayer photoresist laminate has good solubility in any of the photoresist film and the inorganic photoresist underlayer film, but it is not possible to peel off both well. [Examples 6 to 10] The composition shown in Table 2 below is To the composition described in Example 1, 100 ppm (about 1.8 mmol/L) to 500 ppm (about 8.9 mmol/L) of potassium hydroxide and 500 ppm (about 12.5 mmol/L) of sodium hydroxide were added. Further, the peeling property of the inorganic photoresist underlayer film is evaluated. Further, potassium hydroxide and sodium hydroxide are generally used as commercially available reagents, and the number in the table is expressed in units of mass% unless otherwise specified. [*2] (8) Quaternary ammonium hydroxide (Β) water-soluble organic Dropping agent (C) Water (D) Picking brewing (ppm) Peeling property of inorganic photoresist underlayer film Imin 2ίήη 3πάη 4min 5πάη Example 1 1MAH (12.5) ΕΜ90 (50) (37.5) H0H (0) XXXX 〇Implementation Example 6 ΊΜΑΗ (12·5) CMS0 (10) (37.5) m (100) XX 〇〇〇 Example 7 ΊΜΑΗ (12.5) (50) (37.5) Coffee (200) X 〇〇〇〇 Example 8 ΊΜΑΗ (12.5) OGO (10) (37.5) Κ0Η (300) X 〇〇〇〇 Example 9 WU (12 5) m3 (50) (37.5) m (500) 〇〇〇〇〇 Example 10 ΤΕΑΗ (12.5) CMS0 (50) ( 37.5) Fine (500) 〇ο 〇ο 〇. -26- 201106117 ΤΜΑΗ: tetramethylammonium hydroxide ΤΕΑΗ: tetraethylammonium hydroxide DMSO: dimethyl sulfoxide <Evaluation> [Inorganic photoresist underlayer film Peeling property: An organic photoresist underlayer film forming material was applied onto a 20 cm wafer, and heated at 250 ° C for 90 seconds to form an organic photoresist underlayer film having a thickness of 300 nm. The film forming material is a composition unit derived from 100 parts by mass of 1-adamantyl methacrylate and a structure derived from p-hydroxystyrene. A copolymer of 60:40 in molar ratio (Mw = 6000) '20 parts by mass of a glycol urea-based crosslinking agent (product name: NIKALAC MX270, manufactured by Sanwa Chemical Co., Ltd.), 〇· 〇 5 parts by mass of surfactant (product name: XR104, manufactured by Dainippon Ink Chemical Co., Ltd.), 1. 〇 by mass of additive (product name: Catalyst 602, manufactured by Sakamoto Technology Co., Ltd.) dissolved in PGMEA/EL = 6 In the mixed solvent of /4, the solid content concentration was adjusted to 14.3% by mass. Next, the composition for forming an inorganic photoresist underlayer film was spin-coated on the organic photoresist underlayer film at 500 rpm for 1 second, followed by spin coating at 100 rpm for 30 seconds, and heating at 100 ° C for 1 minute, followed by The film was heated at 400 ° C for 30 minutes to form an inorganic photoresist underlayer film having a film thickness of 140 nm. Further, the composition for forming an inorganic photoresist underlayer film is 100 parts by mass or less of resin C (mass average molecular weight: 9400), 0.3 parts by mass of -27-201106117 of cetyltrimethylammonium acetate, and 0.75 mass. The malonic acid was added to a mixed solvent of PGMEA/EL = 6/4, and the polymer solid content concentration of the resin C was adjusted to 2.5% by mass. Resin C [Chemical 9]

The number of constituent units of each resin in the lower right part indicates the existence ratio (mol ratio) of each constituent unit. The laminate of the organic photoresist underlayer film and the inorganic photoresist underlayer film was immersed in the stripping solution for the multilayer photoresist layer of Example 1 and Examples 6 to 10 at 25 ° C for 1 minute to 5 minutes, or less. The reference is used to evaluate the presence or absence of an inorganic photoresist underlayer film. The results are shown in Table 2. 〇: The film can be completely removed. X: The film residue is confirmed. From the above results, it is understood that the inorganic base film can be more preferably peeled off by adding the inorganic base to the peeling liquid for a multilayer photoresist laminate of the present invention.

Claims (1)

201106117 VII. Patent application scope: 1. A multi-layer photoresist laminate stripping solution for forming an inorganic photoresist underlayer film formed directly on a substrate or through other layers and formed on the underlying layer of the inorganic photoresist a multilayer photoresist layer for a photoresist film on a film, the stripping liquid for removing the multilayer photoresist film for the inorganic photoresist underlayer film and the photoresist film, characterized in that: (A) quaternary ammonium hydroxide (B) a water-soluble organic solvent and (C) water. The peeling liquid for a multilayer photoresist laminate according to the first aspect of the invention, which contains 0.1% by mass or more and 20% by mass or less of the above-mentioned (A) fourth-stage saddle hydroxide. 3. The peeling liquid for a multilayer photoresist laminate according to claim 1 or 2, wherein the (A) quaternary ammonium hydroxide is a compound represented by the following formula (1): [NWRaR4] ] OH - . . . (1) [In the above formula (1), R1 to R4 are an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group]. 4. The stripping solution for a multilayer photoresist laminate according to any one of claims 1 to 3, wherein the (A) quaternary ammonium hydroxide is selected from the group consisting of tetramethylammonium hydroxide and tetraethylammonium hydroxide. At least one of the group consisting of ammonium amide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltripropylammonium hydroxide, and methyltributylammonium hydroxide. The peeling liquid for a multilayer photoresist layer according to any one of claims 1 to 4, further comprising (D) an anticorrosive agent. [.S]: -29 - 201106117 6 • If the peeling liquid for the patent application is applied, it is _ 7· as the peeling liquid for the patent application, in which _ is above. The multilayer photoresist layer of any one of items 1 to 5 further contains (E) an inorganic base. The multilayer photoresist layer of any one of the above items 1 to 6 has a pH of 10 for the stripping liquid for the multilayer photoresist layer. 8. The multilayer photoresist layer of any one of items 1 to 7 is as claimed in claim 1 For the combined stripping solution, the inorganic photoresist underlayer film is composed of a siloxane polymer. A method for treating a multilayer photoresist layer, which comprises using the stripping liquid for a multilayer photoresist laminate according to any one of claims 1 to 8, which has an inorganic layer formed directly on the substrate or through other layers. A multilayer photoresist layer of a photoresist underlayer film and a photoresist film formed on the inorganic photoresist underlayer film to remove the photoresist film and the inorganic photoresist underlayer film. -30- 201106117 IV Designated representative map: (1) The representative representative of the case is: None. (II) Simple description of the symbol of the representative figure: None 201106117 V. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: none