JP2018081307A - Treatment liquid and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pattern forming method capable of forming a pattern with few development defects, and a treatment liquid used for the method.SOLUTION: The pattern forming method according to the present invention includes the steps of: (a) forming a film using an actinic ray-sensitive or radiation-sensitive composition; (b) exposing the film; and (c) treating the exposed film using the treatment liquid. The treatment liquid contains an organic solvent having a standard boiling point of 172°C or higher, and the content of the solvent in the treatment liquid is 30 mass% or more.SELECTED DRAWING: None

Description

The present invention relates to a processing liquid and a pattern forming method.
More specifically, the present invention is used in a semiconductor manufacturing process such as an IC (Integrated Circuit), a circuit board such as a liquid crystal and a thermal head, and a lithography process for other photofabrication. The present invention relates to a processing liquid and a pattern forming method.

Conventionally, in a manufacturing process of a semiconductor device such as an IC (Integrated Circuit) or an LSI (Large Scale Integrated circuit), fine processing by lithography using a photoresist composition has been performed. In recent years, with the high integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quarter micron region has been required. Along with this, there is a tendency to shorten the exposure wavelength from g-line to i-line, and further to KrF excimer laser light. Furthermore, in addition to excimer laser light, lithography using electron beams, X-rays, or EUV light (Extreme Ultra Violet, extreme ultraviolet rays) is also under development.
In such lithography, a film is formed with a photoresist composition (also called an actinic ray or radiation sensitive composition or a chemically amplified resist composition), and then the resulting film is developed with a developer. The film after development is washed with a rinse solution.
For example, Patent Document 1 discloses that an organic processing solution containing a mixture of a first organic solvent and a second organic solvent selected from a ketone solvent and an ester solvent is used as a developing solution. .

JP 2012-181523 A

  In recent years, with the high integration of integrated circuits, the formation of fine patterns using a photoresist composition is required. In the formation of such a fine pattern, since a slight defect affects the operation of the semiconductor chip, a developing solution and a rinsing solution that do not cause a defect are required. On the other hand, in the C / H pattern (contact hole pattern), the hole diameter of the contact hole is narrowed with the miniaturization, so that the “edge defect” that the edge of the hole is connected or the hole is not opened at all is likely to occur. . The developing solution and the rinsing solution are not limited to the types of patterns such as the L / S pattern and the C / H pattern, and are required to exhibit good performance, and development that can eliminate the occurrence of defective defects and low defect performance at the same time. Liquids and rinse liquids were sought.

  However, at present, a developing solution and a rinsing solution that can simultaneously suppress the occurrence of defective defects and low defect performance in a fine pattern are not yet known.

  The present invention has been made in view of the above points, and provides a processing liquid and a pattern formation method for resist film patterning that can simultaneously suppress the occurrence of defects on a resist and the occurrence of omission defects in a resist C / H pattern. The purpose is to do.

  As a result of intensive studies on the above problems, the present inventors have found that a desired effect can be obtained by using a treatment liquid containing an organic solvent having a specific boiling point in a specific range.

ADVANTAGE OF THE INVENTION According to this invention, the processing liquid and pattern formation method for resist film patterning which can suppress the defect generation | occurrence | production on a resist and generation | occurrence | production of the defect defect in a resist C / H pattern simultaneously can be provided.
That is, the present invention provides the following [1] to [20].
[1] (a) a step of forming a resist film using an actinic ray-sensitive or radiation-sensitive composition, (b) a step of exposing the film, and (c) the film exposed using a treatment liquid. The pattern formation method including the process of processing, Comprising: The said process liquid contains 30 mass% or more of organic solvents whose standard boiling point is 172 degreeC or more.
[2] The pattern forming method according to [1], wherein the organic solvent has a standard boiling point of 175 ° C. or higher.
[3] The pattern forming method according to [1] or [2], wherein the step (c) includes a step of developing the exposed film using the processing solution.
[4] The step (c) includes a step of developing the exposed film and a step of rinsing the developed film. In at least one of the developing step and the rinsing step, the processing is performed. The pattern forming method according to [1] or [2], wherein a liquid is used.
[5] The pattern forming method according to any one of [1] to [4], wherein the treatment liquid further includes an ester solvent.
[6] The ester solvent is butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, butyl isobutanoate, and butanoic acid. The pattern forming method according to [5], including at least one selected from butyl.
[7] The pattern forming method according to any one of [1] to [4], wherein the treatment liquid further includes a ketone solvent.
[8] The pattern forming method according to [7], wherein the ketone solvent contains at least one selected from methyl isoamyl ketone, cyclohexane, cyclopentanone, methyl ethyl ketone, and 2-heptanone.
[9] The composition includes any one of [1] to [8], comprising a resin having a group that decomposes by the action of an acid to generate a polar group, and a compound that generates an acid upon irradiation with actinic rays or radiation. A pattern forming method according to any one of the above.
[10] The pattern forming method according to any one of [1] to [9], wherein the step (b) is performed using a KrF or ArF excimer laser.
[11] The pattern forming method according to any one of [1] to [9], wherein the step (b) is performed using EUV light.
[12] The pattern forming method according to any one of [1] to [11], further comprising: (d) heating the film processed using the processing solution.
[13] The pattern forming method according to any one of [1] to [11], wherein the treatment liquid contains 0.001 to 30 ppm by mass of organic impurities having a boiling point of 300 ° C. or higher with respect to the total mass of the treatment liquid.
[14] The pattern forming method according to any one of [1] to [13], wherein the water content of the treatment liquid is 500 ppm or less.
[15] A treatment liquid used in the pattern forming method according to any one of [1] to [14], wherein the treatment liquid contains 30% by mass or more of an organic solvent having a standard boiling point of 172 ° C. or higher.
[16] The processing solution according to [15], which is used for developing the exposed film.
[17] The processing solution according to [15], which is used for rinsing the developed film.
[18] The processing liquid according to any one of [15] to [17], wherein the processing liquid contains 0.001 to 30 ppm by mass of organic impurities having a boiling point of 300 ° C. or higher with respect to the total mass of the processing liquid.
[19] The treatment liquid contains an element selected from the group consisting of Fe, Cr, Ni and Pb, and the content of each element is 0.001 to 100 mass ppt with respect to the total mass of the treatment liquid [ 15] to [18].
[20] The treatment liquid according to any one of [15] to [19], which is produced through a distillation and filtration process.

It is an organic solvent purifier.

Hereinafter, embodiments of the present invention will be described in detail. Conventionally, as a negative pattern forming method, forming a film on a substrate using a resist composition, exposing the film, and processing the exposed film using a processing liquid A method including the above is known.
The present inventors have found that development defects are relatively likely to occur when a pattern is formed using this conventional method. As a result of diligent examination of the reason, it has been found for the first time that many of these development defects are derived from the processing solution used for processing the exposed film. And it discovered that a development defect could be reduced significantly by determining the composition of the said processing liquid as follows.

<Processing liquid>
The treatment liquid according to the present invention includes (1) 30% by mass or more of an organic solvent having a standard boiling point of 172 ° C. or higher.

The processing solution of the present invention is preferably used as a developing solution and / or a rinsing solution. When the treatment liquid of the present invention is used, since the volatilization rate is relatively slow, the effect of washing away the insoluble matter adhering to the substrate, film or pattern is increased. As a result, development defects can be reduced. Furthermore, it has been found that in addition to the effect of suppressing development defects, the lithography performance (removability) is also improved. That is, it has been found that both defect performance and lithography performance can be achieved. Although the cause of this is not clear, the present inventors speculate as follows.
When the processing liquid of the present invention is used, the standard boiling point is as high as 172 ° C. or higher, so that the drying speed of the processing liquid at the wear edge portion can be slowed. It is considered that the drying of the wafer can be made more uniform in the wafer plane. When the drying speed is low, the film density is relatively high. Therefore, when the substrate side is etched using the formed pattern, it is assumed that the etching speed by the etching gas is low. That is, by containing 30% by mass or more of an organic solvent having a standard boiling point of 172 ° C. or higher as the processing liquid, the difference in the drying speed of the developer and / or the rinsing liquid within the wafer surface can be further reduced. . As a result, it is presumed that in-plane uniformity such as line width or hole diameter in the wafer surface after etching can be further improved.
In the processing solution of the present invention, the organic solvent having a normal boiling point of 172 ° C. or more is adjusted to 95% by mass or less. This is preferable from the viewpoint of reducing the deterioration of the pattern shape due to the reduction of the omission. Although the cause of the deterioration of the pattern shape is not clear, it is assumed that the pattern shape changes due to urging deformation of the resist resin in the pattern portion during baking due to the plasticizing effect by the residual solvent. In addition, content of the organic solvent whose standard boiling point with respect to a process liquid is 172 degreeC or more becomes like this. Preferably it is 30-80 mass%, More preferably, you may be 30-60 mass%. By setting the organic solvent having a standard boiling point of 172 ° C. or higher to the processing solution in such a range, development defects can be further reduced.

As an organic solvent whose standard boiling point is 172 degreeC or more, what is shown in following Table 1 is mentioned, for example. Table 1 also shows the standard boiling points of each.

  The organic solvent contained in the treatment liquid according to the present invention preferably has a standard boiling point of 175 ° C. or higher, and more preferably has a standard boiling point of 200 ° C. or higher. The upper limit of the standard boiling point of the organic solvent contained in the treatment liquid is not limited, but is preferably less than 300 ° C.

  In addition, the said process liquid may contain only 1 type of organic solvents whose standard boiling point is 172 degreeC or more, and may contain 2 or more types of said organic solvents.

  The treatment liquid according to the present invention may further contain an organic solvent having a standard boiling point of less than 172 ° C. The treatment liquid according to the present invention preferably contains a combination of γ-butyrolactone and butyl acetate.

  Hereinafter, although various organic solvents are shown, this invention is not limited to this. As the organic solvent, solvents such as ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents and the like can be used. The organic solvent contained in the treatment liquid of the present invention preferably contains an organic solvent having a standard boiling point of 172 ° C. or higher and an ester solvent or a ketone solvent.

  In particular, a treatment liquid containing at least one solvent selected from ketone solvents, ester solvents, alcohol solvents and ether solvents is preferable.

  Examples of the ester solvent include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, propyl acetate, isopropyl acetate, amyl acetate (pentyl acetate), isoamyl acetate (isopentyl acetate, 3-methylbutyl acetate), and acetic acid 2 -Methylbutyl, 1-methylbutyl acetate, hexyl acetate, isohexyl acetate, heptyl acetate, octyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), ethylene glycol mono Ethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethyl Lenglycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl -3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2 -Methoxypentyl acetate, 3-methoxypentyl Acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol Diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, aceto Methyl acetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, pentyl propionate, hexyl propionate, heptyl propionate, Butyl tanoate, isobutyl butanoate, pentyl butanoate, hexyl butanoate, isobutyl isobutanoate, propyl pentanoate, isopropyl pentanoate, butyl pentanoate, pentyl pentanoate, ethyl hexanoate, propyl hexanoate, butyl hexanoate, hexanoic acid Isobutyl, methyl heptanoate, ethyl heptanoate, propyl heptanoate, cyclohexyl acetate, cycloheptyl acetate, 2-ethylhexyl acetate, cyclopentyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypro Pionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate and the like can be mentioned. Among these, butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, butyl butanoate, and butyl isobutanoate are preferably used. Butyl acetate, isoamyl acetate or butyl isobutanoate is particularly preferably used.

  Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, Phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate, γ-butyrolactone, methyl isoamyl ketone, cyclopentanone, 2 , 5-dimethyl-4-hexanone, among which methyl isoamyl ketone, cyclohexane, cyclopentanone, methyl ethyl ketone, and 2-heptone Non are preferably used, methyl isoamyl ketone, cyclohexane, 2-heptanone are used more preferably, methyl isoamyl ketone, 2-heptanone are particularly preferred.

  Examples of alcohol solvents include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1 -Hexanol, 1-heptanol, 1-octanol, 1-decanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, 3-methyl-3-pen Tanol, cyclopentanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-2- Pentanol, 3-methyl-3-pentanol, 4-methyl-2 Pentanol, 4-methyl-3-pentanol, cyclohexanol, 5-methyl-2-hexanol, 4-methyl-2-hexanol, 4,5-dimethyl-2-hexanol, 6-methyl-2-heptanol, 7 -Alcohol (monohydric alcohol) such as methyl-2-octanol, 8-methyl-2-nonanol, 9-methyl-2-decanol, 3-methoxy-1-butanol, ethylene glycol, diethylene glycol, triethylene glycol, etc. Glycol solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol), diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbutanol, Glycol ether solvents containing hydroxyl groups such as tylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, etc. Can be mentioned. Among these, it is preferable to use a glycol ether solvent.

  Examples of ether solvents include glycol ether solvents containing hydroxyl groups, glycol ether solvents that do not contain hydroxyl groups such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether, anisole, and phenetole. Aromatic ether solvents, dioxane, tetrahydrofuran, tetrahydropyran, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane, isopropyl ether and the like. Preferably, an glycol ether solvent or an aromatic ether solvent such as anisole is used.

  Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.

Examples of the hydrocarbon solvent include pentane, hexane, octane, nonane, decane, dodecane, undecane, hexadecane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, perfluorohexane, and perfluoroheptane. Aliphatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, dipropylbenzene, etc. And aromatic hydrocarbon solvents.
Further, as the hydrocarbon solvent, an unsaturated hydrocarbon solvent can also be used, and examples thereof include unsaturated hydrocarbon solvents such as octene, nonene, decene, undecene, dodecene, hexadecene and the like. The number of double bonds and triple bonds of the unsaturated hydrocarbon solvent is not particularly limited, and the unsaturated hydrocarbon solvent may have any position in the hydrocarbon chain. Further, when the unsaturated hydrocarbon solvent has a double bond, a cis isomer and a trans isomer may be mixed.
The aliphatic hydrocarbon solvent that is a hydrocarbon solvent may be a mixture of compounds having the same number of carbon atoms and different structures. For example, when decane is used as the aliphatic hydrocarbon solvent, 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, isooctane, etc., which are compounds having the same carbon number and different structures, are aliphatic hydrocarbon solvents. May be included.
In addition, the compounds having the same number of carbon atoms and different structures may include only one kind or plural kinds as described above.

<Developer and rinse solution that can be used together with processing solution>
Hereinafter, the developing solution and the rinsing solution that can be used together with the processing solution of the present invention will be described in detail.
The developer that can be used in combination with the processing solution of the present invention will be described in detail.
In the case of using EUV light (Extreme Ultra Violet) and EB (Electron Beam) in an exposure process described later, the developer has 6 or more carbon atoms (preferably 6 to 14 carbon atoms) from the point that swelling of the resist film can be suppressed. 6 to 12 is more preferable, and 6 to 10 is still more preferable), and it is preferable to use an ester solvent having 2 or less hetero atoms.
The hetero atom of the ester solvent is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, and a sulfur atom. The number of heteroatoms is preferably 2 or less.
Preferred examples of ester solvents having 6 or more carbon atoms and 2 or less heteroatoms include butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, and propionic acid. It is preferably at least one selected from hexyl, heptyl propionate, butyl butanoate, and butyl isobutanoate, and particularly preferably isoamyl acetate or butyl isobutanoate is used.

In the case where EUV light and EB are used in the exposure process described later, the developer is replaced with the ester solvent and the hydrocarbon solvent instead of the ester solvent having 6 or more carbon atoms and 2 or less hetero atoms. A mixed solvent of solvents, or a mixed solvent of the ketone solvent and the hydrocarbon solvent may be used. Even in this case, it is effective in suppressing the swelling of the resist film.
When an ester solvent and a hydrocarbon solvent are used in combination, isoamyl acetate is preferably used as the ester solvent. As the hydrocarbon solvent, it is preferable to use a saturated hydrocarbon solvent (for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.) from the viewpoint of adjusting the solubility of the resist film.
In the case where a ketone solvent and a hydrocarbon solvent are used in combination, it is preferable to use diisobutyl ketone and 2,5-dimethyl-4-hexanone as the ketone solvent. As the hydrocarbon solvent, it is preferable to use a saturated hydrocarbon solvent (for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.) from the viewpoint of adjusting the solubility of the resist film.
In the case of using the above mixed solvent, the content of the hydrocarbon solvent is not particularly limited because it depends on the solvent solubility of the resist film, and the necessary amount may be determined by appropriately preparing.

A plurality of the above organic solvents may be mixed, or may be used by mixing with other solvents or water. From the viewpoint of achieving the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, more preferably 500 ppm or less, still more preferably 300 ppm or less, and 150 ppm or less. Even more preferably, it is even more preferable that it does not substantially contain water, while it is preferable that it contains a trace amount of water of 5 ppm or more due to another factor described later.
In addition, the water content is preferably 500 ppm or less from the viewpoint of the shape after processing when the substrate side is processed using the resist pattern formed after the development or rinsing with the processing solution according to the present invention as an etching mask. . When the water content is 500 ppm or less, the pattern can be more easily removed and the pattern resolution can be further improved. Although the mechanism that can further improve the release property is not clear, the solubility of the resist resin component that dissolves in the processing solution such as the developing solution or the rinsing solution can be reduced by suppressing the water content at the time of the developing processing or the rinsing processing. Since it can be maintained uniformly, resist resin can be prevented from precipitating or adhering to the substrate during development, rinsing, or drying treatment, and a good pattern shape and good resolution can be obtained. It is possible to improve resist removal and maintain in-plane uniformity.
Further, the lower limit of the moisture content is set to 5 ppm or more from the viewpoint of reducing the influence on defects and roughness after etching, or changes in physical properties such as electrical characteristics of the substrate material due to migration to the underlayer. preferable. These factors are not clear, but due to the trace amount of water contained in the treatment liquid, inorganic impurities (ionic components, and ionic components, which are unevenly distributed on the surface of the resist resin pattern or resist underlayer film to be treated) Hydrophilic inorganic particle components) can be taken into the processing solution and removed, resulting in changes in physical properties such as the effects on post-etching defects and roughness, or electrical properties of the substrate material due to migration to the underlying layer. It is assumed that it can be reduced.
The concentration of the organic solvent in the developer (total in the case of mixing) is preferably 50 to 100% by mass, more preferably 85 to 100% by mass, still more preferably 90 to 100% by mass, and particularly preferably 95 to 100%. % By mass. Most preferably, it consists essentially of an organic solvent. In addition, the case where it consists only of an organic solvent includes the case where a trace amount surfactant, antioxidant, stabilizer, an antifoamer, etc. are contained.

  Moreover, as an organic solvent used as a developing solution, in addition to the ester solvent described above, an ester solvent represented by the general formula (S1) or general formula (S2) described later can also be suitably exemplified. As the ester solvent, it is even more preferable to use a solvent represented by the general formula (S1), and it is particularly preferable to use alkyl acetate, and butyl acetate, amyl acetate (pentyl acetate), isoamyl acetate (acetic acid). Most preferably, isopentyl) is used.

R ⁰ —C (═O) —O—R ¹ General Formula (S1)

In the general formula (S1), R ⁰ and R ¹ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group, or a halogen atom. . R ⁰ and R ¹ may combine with each other to form a ring.
The carbon number of the alkyl group, alkoxyl group and alkoxycarbonyl group for R ⁰ and R ¹ is preferably in the range of 1 to 15, and the carbon number of the cycloalkyl group is preferably 3 to 15.
R ⁰ and R ¹ are preferably a hydrogen atom or an alkyl group, and are formed by bonding an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, or R ⁰ and R ^{1 with} respect to R ⁰ and R ^1. The ring may be substituted with a hydroxyl group, a group containing a carbonyl group (for example, an acyl group, an aldehyde group, alkoxycarbonyl, etc.), a cyano group, or the like.

  Examples of the solvent represented by the general formula (S1) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, and butyl lactate. , Propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, propion Examples include isopropyl acid, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, and the like.

Of these, R ⁰ and R ¹ are preferably unsubstituted alkyl groups.
The solvent represented by the general formula (S1) is preferably alkyl acetate, more preferably butyl acetate, amyl acetate (pentyl acetate), or isoamyl acetate (isopentyl acetate), and preferably isoamyl acetate. Further preferred.

  The solvent represented by the general formula (S1) may be used in combination with one or more other organic solvents. The combined solvent in this case is not particularly limited as long as it can be mixed without being separated into the solvent represented by the general formula (S1), and the solvents represented by the general formula (S1) may be used in combination. The solvent represented by the general formula (S1) may be used by mixing it with a solvent selected from other ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents and hydrocarbon solvents. Good. One or more solvents can be used in combination, but it is preferable to use one solvent in order to obtain stable performance. The mixing ratio of the solvent represented by the general formula (S1) and the combined solvent in the case of using one mixed solvent together is usually 20:80 to 99: 1, preferably 50:50 to 97: by mass ratio. 3, more preferably 60:40 to 95: 5, most preferably 60:40 to 90:10.

  As the organic solvent used as the developer, a glycol ether solvent can be used. As the glycol ether solvent, a solvent represented by the following general formula (S2) may be used.

R ² —C (═O) —O—R ³ —O—R ⁴ Formula (S2)

In the general formula (S2), R ² and R ⁴ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group, or a halogen atom. . R ² and R ⁴ may combine with each other to form a ring.
R ² and R ⁴ are preferably a hydrogen atom or an alkyl group. The carbon number of the alkyl group, alkoxyl group and alkoxycarbonyl group for R ² and R ⁴ is preferably in the range of 1 to 15, and the carbon number of the cycloalkyl group is preferably 3 to 15.
R ³ represents an alkylene group or a cycloalkylene group. R ³ is preferably an alkylene group. The number of carbon atoms of the alkylene group for R ³ is preferably in the range of 1-10. The number of carbon atoms of the cycloalkylene group for R ³ is preferably in the range of 3-10.
The alkyl group, cycloalkyl group, alkoxyl group, alkoxycarbonyl group for R ² and R ⁴ , the alkylene group, cycloalkylene group for R ³ , and the ring formed by bonding R ² and R ⁴ to each other are a hydroxyl group , A group containing a carbonyl group (for example, an acyl group, an aldehyde group, alkoxycarbonyl, etc.), a cyano group or the like may be substituted.

In general formula (S2), the alkylene group for R ³ may have an ether bond in the alkylene chain.

Examples of the solvent represented by the general formula (S2) include propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl. Ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl-3-methoxy Propionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, ethyl methoxyacetate, ethyl ethoxyacetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4 -Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3 -Methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4- Chill -4-methoxy pentyl acetate and the like, it is preferably a propylene glycol monomethyl ether acetate.
Among these, R ² and R ⁴ are preferably unsubstituted alkyl groups, R ³ is preferably an unsubstituted alkylene group, and R ² and R ⁴ are either a methyl group or an ethyl group. More preferably, R ² and R ⁴ are even more preferably methyl groups.

  The solvent represented by the general formula (S2) may be used in combination with one or more other organic solvents. The combined solvent in this case is not particularly limited as long as it can be mixed without being separated into the solvent represented by the general formula (S2), and the solvents represented by the general formula (S2) may be used in combination. The solvent represented by the general formula (S2) may be used by mixing it with a solvent selected from other ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents and hydrocarbon solvents. Good. One or more solvents can be used in combination, but it is preferable to use one solvent in order to obtain stable performance. The mixing ratio of the solvent represented by the general formula (S2) and the combined solvent when the combined solvent is used is usually 20:80 to 99: 1, preferably 50:50 to 97: 3, more preferably 60:40 to 95: 5, most preferably 60:40 to 90:10.

  Moreover, as an organic solvent used as a developing solution, in addition to the ether solvent described above, an ether solvent containing one or more aromatic rings can also be suitably exemplified. Among these, a solvent represented by the following general formula (S3) is more preferable, and anisole is most preferable.

In the general formula (S3), R _S represents an alkyl group. The alkyl group preferably has 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and most preferably a methyl group.

  As an organic solvent contained in a developing solution, the organic solvent used for the actinic-ray-sensitive or radiation-sensitive composition mentioned later can be used.

The rinse liquid that can be used in combination with the treatment liquid of the present invention will be described in detail.
The organic solvent contained in the rinsing liquid may be an embodiment in which at least one selected from the group consisting of the ester solvent and the ketone solvent is used from the viewpoint that it is particularly effective for reducing residues after development. Good.
When the rinse liquid contains at least one selected from the group consisting of ester solvents and ketone solvents, butyl acetate, isopentyl acetate (isoamyl acetate), n-pentyl acetate, ethyl 3-ethoxypropionate (EEP, Ethyl-3-ethoxypropionate) and at least one solvent selected from the group consisting of 2-heptanone as a main component, preferably at least selected from the group consisting of butyl acetate and 2-heptanone It is particularly preferable to contain one solvent as a main component.
When the rinsing liquid contains at least one selected from the group consisting of ester solvents and ketone solvents, the rinse liquid is selected from the group consisting of ester solvents, glycol ether solvents, ketone solvents, alcohol solvents. It is preferable to contain propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl acetate, ethyl lactate, methyl 3-methoxypropionate, cyclohexanone, methyl ethyl ketone, γ- A solvent selected from the group consisting of butyrolactone, propanol, 3-methoxy-1-butanol, N-methylpyrrolidone and propylene carbonate is preferred.
Among these, when an ester solvent is used as the organic solvent, it is preferable to use two or more ester solvents from the viewpoint that the above effect is further exhibited. As a specific example in this case, an ester solvent (preferably butyl acetate) is used as a main component, and an ester solvent (preferably propylene glycol monomethyl ether acetate (PGMEA)) having a different chemical structure is used as a subcomponent. Can be mentioned.
When an ester solvent is used as the organic solvent, a glycol ether solvent may be used in addition to the ester solvent (one type or two or more types) from the viewpoint that the above effect is further exhibited. Specific examples in this case include using an ester solvent (preferably butyl acetate) as a main component and a glycol ether solvent (preferably propylene glycol monomethyl ether (PGME)) as a subcomponent.
When a ketone solvent is used as the organic solvent, an ester solvent and / or a glycol ether solvent is used in addition to the ketone solvent (one or two or more) from the viewpoint that the above effects are further exhibited. May be. Specific examples in this case include a ketone solvent (preferably 2-heptanone) as a main component, an ester solvent (preferably propylene glycol monomethyl ether acetate (PGMEA)) and / or a glycol ether solvent (preferably propylene). Glycol monomethyl ether (PGME)) is used as an accessory component.
Here, said "main component" means that content with respect to the total mass of an organic solvent is 50-100 mass%, Preferably it is 70-100 mass%, More preferably, it is 80-100 mass%, More preferably, it means 90 to 100% by mass, particularly preferably 95 to 100% by mass.
Moreover, when it contains a subcomponent, it is preferable that content of a subcomponent is 0.1-20 mass% with respect to the total mass (100 mass%) of a main component, 0.5-10 More preferably, it is 1 mass%, and it is still more preferable that it is 1-5 mass%.

  Hereinafter, various additives that the treatment liquid of the present invention may contain will be described in detail. The following various additives may, of course, be included in the developer and / or rinse solution that can be used in combination with the above-described processing solution of the present invention.

<Surfactant>
The treatment liquid may contain a surfactant. Thereby, the wettability with respect to the resist film is improved, and the development and / or rinsing proceeds more effectively.
As the surfactant, the same surfactants as those used in the actinic ray-sensitive or radiation-sensitive composition described later can be used.
Content of surfactant is 0.001-5 mass% normally with respect to the total mass of a process liquid, Preferably it is 0.005-2 mass%, More preferably, it is 0.01-0.5 mass%. .

  As the surfactant, an anionic surfactant, a nonionic surfactant, and a cationic surfactant are preferable, and a nonionic surfactant is more preferable.

  The treatment liquid for semiconductor production according to the present invention contains, as a surfactant, at least one surfactant selected from the group consisting of an anionic surfactant, a nonionic surfactant and a cationic surfactant. The wettability with respect to the resist film is improved, and development and / or rinsing proceeds more effectively.

  An additive may contain 2 or more types in combination.

[2-1] Anionic surfactants Anionic surfactants include, for example, alkyl sulfates, alkyl sulfonic acids, alkyl benzene sulfonic acids, alkyl naphthalene sulfonic acids, alkyl diphenyl ether sulfonic acids, polyoxyethylene alkyl ether carboxylic acids, polyoxyethylenes. Examples include alkyl ether acetic acid, polyoxyethylene alkyl ether propionic acid, polyoxyethylene alkyl ether sulfuric acid, polyoxyethylene aryl ether acetic acid, polyoxyethylene aryl ether propionic acid, polyoxyethylene aryl ether sulfuric acid, and salts thereof. .
The anionic surfactant is not particularly limited, but alkyl sulfate, polyoxyethylene aryl ether sulfate, and polyoxyethylene alkyl ether sulfate are preferable, and polyoxyethylene aryl ether sulfate is more preferable.

[2-2] Nonionic surfactant Nonionic surfactants include, for example, polyalkylene oxide alkylphenyl ether surfactants, polyalkylene oxide alkyl ether surfactants, and block polymer interfaces composed of polyethylene oxide and polypropylene oxide. Activators, polyoxyalkylene distyrenated phenyl ether surfactants, polyalkylene tribenzylphenyl ether surfactants, acetylene polyalkylene oxide surfactants, and the like.

[2-3] Cationic surfactant Examples of the cationic surfactant include a quaternary ammonium salt surfactant and an alkylpyridium surfactant.

Quaternary ammonium salt surfactants include, for example, tetramethylammonium chloride, tetrabutylammonium chloride, dodecyldimethylbenzylammonium chloride, alkyltrimethylammonium chloride, octyltrimethylammonium chloride, decyltrimethylammonium chloride, dodecyltrimethylammonium chloride, chloride Examples include tetradecyltrimethylammonium chloride, cetyltrimethylammonium chloride, and stearyltrimethylammonium chloride. The quaternary ammonium salt surfactant is not particularly limited, but is preferably dodecyldimethylbenzylammonium chloride.
These surfactants may be used alone or in several combinations.

<Antioxidant>
The treatment liquid may contain an antioxidant.

As the antioxidant, known ones can be used, but when used for semiconductor applications, amine-based antioxidants and phenol-based antioxidants are preferably used.
Examples of amine-based antioxidants include 1-naphthylamine, phenyl-1-naphthylamine, p-octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, p-dodecylphenyl-1-naphthylamine, and phenyl-2. -Naphthylamine antioxidants such as naphthylamine; N, N'-diisopropyl-p-phenylenediamine, N, N'-diisobutyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N ' -Di-β-naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-1,3-dimethylbutyl-N '-Phenyl-p-phenylenediamine, dioctyl-p-phenyle Phenylenediamine antioxidants such as diamine, phenylhexyl-p-phenylenediamine, phenyloctyl-p-phenylenediamine; dipyridylamine, diphenylamine, p, p'-di-n-butyldiphenylamine, p, p'-di- t-butyldiphenylamine, p, p'-di-t-pentyldiphenylamine, p, p'-dioctyldiphenylamine, p, p'-dinonyldiphenylamine, p, p'-didecyldiphenylamine, p, p'-didodecyl Diphenylamine oxidation such as diphenylamine, p, p'-distyryldiphenylamine, p, p'-dimethoxydiphenylamine, 4,4'-bis (4-α, α-dimethylbenzoyl) diphenylamine, p-isopropoxydiphenylamine, dipyridylamine Inhibitor; phenothiazi And phenothiazine antioxidants such as N-methylphenothiazine, N-ethylphenothiazine, 3,7-dioctylphenothiazine, phenothiazinecarboxylic acid ester and phenoselenadine.
Examples of the phenolic antioxidant include 2,6-di-tert-butylphenol (hereinafter, tertiary butyl is abbreviated as t-butyl), 2,6-di-t-butyl-p-cresol, 2 , 6-Di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4-dimethyl-6-tert-butylphenol, 4,4′-methylenebis (2, 6-di-t-butylphenol), 4,4'-bis (2,6-di-t-butylphenol), 4,4'-bis (2-methyl-6-t-butylphenol), 2,2'- Methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4 , 4 ' -Isopropylidenebis (2,6-di-t-butylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (4-methyl-6-nonylphenol), 2 , 2′-isobutylidenebis (4,6-dimethylphenol), 2,6-bis (2′-hydroxy-3′-t-butyl-5′-methylbenzyl) -4-methylphenol, 3-t -Butyl-4-hydroxyanisole, 2-t-butyl-4-hydroxyanisole, octyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- (4-hydroxy-3, Stearyl 5-di-t-butylphenyl) propionate, oleyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- (4-hydro Cis-3,5-di-t-butylphenyl) dodecyl propionate, decyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- (4-hydroxy-3,5- Octyl di-t-butylphenyl) propionate, tetrakis {3- (4-hydroxy-3,5-di-t-butylphenyl) propionyloxymethyl} methane, 3- (4-hydroxy-3,5-di-) t-butylphenyl) propionic acid glycerin monoester, ester of 3- (4-hydroxy-3,5-di-t-butylphenyl) propionic acid and glycerin monooleyl ether, 3- (4-hydroxy-3,5 -Di-t-butylphenyl) propionic acid butylene glycol diester, 2,6-di-t-butyl-α-dimethylamino-p-cresol, 2,6-di-t-butyl-4- (N, N′-dimethylaminomethylphenol), tris {(3,5-di-t-butyl-4-hydroxyphenyl) propionyl-oxyethyl} isocyanurate, tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5 -Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3 , 9-bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-teto Raoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-t-butyl-4-hydroxybenzyl) benzene, bis {3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid} glycol ester, and the like.

  Although content of antioxidant is not specifically limited, 0.0001-1 mass% is preferable with respect to the total mass of a process liquid, 0.0001-0.1 mass% is more preferable, 0.0001-0 More preferred is 0.01 mass%. When the content is 0.0001% by mass or more, an excellent antioxidant effect is obtained, and when the content is 1% by mass or less, residues after development and / or rinsing tend to be suppressed.

<Basic compound>
The treatment liquid of the present invention may contain a basic compound. Specific examples of the basic compound include compounds exemplified as the basic compound (E) that can be contained in the actinic ray-sensitive or radiation-sensitive composition described later.
Among the basic compounds that can be contained in the treatment liquid of the present invention, the following nitrogen-containing compounds can be preferably used.

  When the nitrogen-containing compound is contained in the developer, the nitrogen-containing compound interacts with a polar group generated in the resist film by the action of an acid, and can further improve the insolubility of the exposed portion with respect to the organic solvent. Here, the interaction between the nitrogen-containing compound and the polar group includes an action of reacting the nitrogen-containing compound and the polar group to form a salt, an action of forming an ionic bond, and the like.

As said nitrogen-containing compound, the compound represented by Formula (1) is preferable.

In the above formula (1), R ¹ and R ² are each independently a hydrogen atom, a hydroxyl group, a formyl group, an alkoxy group, an alkoxycarbonyl group, a chain hydrocarbon group having 1 to 30 carbon atoms, a carbon number of 3 30 is an alicyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or a group formed by combining two or more of these groups. R ³ is a hydrogen atom, a hydroxyl group, a formyl group, an alkoxy group, an alkoxycarbonyl group, an n-valent chain hydrocarbon group having 1 to 30 carbon atoms, an n-valent alicyclic hydrocarbon group having 3 to 30 carbon atoms, An n-valent aromatic hydrocarbon group having 6 to 14 carbon atoms or an n-valent group formed by combining two or more of these groups. n is an integer of 1 or more. However, when n is 2 or more, the plurality of R ¹ and R ² may be the same or different. Further, any two of R ^{1 to} R ³ may be bonded to form a ring structure together with the nitrogen atom to which each is bonded.

Examples of the C1-C30 chain hydrocarbon group represented by R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and 2-methylpropyl. Group, 1-methylpropyl group, t-butyl group and the like.

Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms represented by R ¹ and R ² include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a norbornyl group.

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R ¹ and R ² include a phenyl group, a tolyl group, and a naphthyl group.

Examples of the group formed by combining two or more of these groups represented by R ¹ and R ² include aralkyl groups having 6 to 12 carbon atoms such as benzyl group, phenethyl group, naphthylmethyl group, and naphthylethyl group. Can be mentioned.

Examples of the n-valent chain hydrocarbon group having 1 to 30 carbon atoms represented by R ³ include groups exemplified as the chain hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ and R ^2. And a group obtained by removing (n-1) hydrogen atoms from the same group.

Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms represented by R ³ include the same groups as those exemplified as the cyclic hydrocarbon group having 3 to 30 carbon atoms represented by R ¹ and R ^2. And a group obtained by removing (n-1) hydrogen atoms from the group.

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R ³ are the same as those exemplified as the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R ¹ and R ² . And a group obtained by removing (n-1) hydrogen atoms from the group.

The group formed by combining two or more of these groups represented by R ³ is the same as the group exemplified as a group formed by combining two or more of these groups represented by R ¹ and R ² . And a group obtained by removing (n-1) hydrogen atoms from the group.

The groups represented by R ^{1 to} R ³ may be substituted. Specific examples of the substituent include a methyl group, an ethyl group, a provir group, an n-butyl group, a t-butyl group, a hydroxyl group, a carboxy group, a halogen atom, and an alkoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Moreover, as an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned, for example.

  Examples of the compound represented by the above formula (1) include (cyclo) alkylamine compounds, nitrogen-containing heterocyclic compounds, amide group-containing compounds, urea compounds and the like.

  Examples of (cyclo) alkylamine compounds include compounds having one nitrogen atom, compounds having two nitrogen atoms, compounds having three or more nitrogen atoms, and the like.

  Examples of (cyclo) alkylamine compounds having one nitrogen atom include mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, 1-aminodecane, cyclohexylamine and the like. Di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine Di (cyclo) alkylamines such as dicyclohexylamine; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri -N-octylamine, tri-n-nonylamine, tri- -Tri (cyclo) alkylamines such as decylamine, cyclohexyldimethylamine, methyldicyclohexylamine, tricyclohexylamine; substituted alkylamines such as triethanolamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methyl Aniline, 3-methylaniline, 4-methylaniline, N, N-dibutylaniline, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine, 2,4,6-tri-tert-butyl-N-methylaniline, N -Phenyldiethanolamine, 2,6-diisopropylaniline, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, etc. Aromatic Ami Kind, and the like.

  Examples of the (cyclo) alkylamine compound having two nitrogen atoms include ethylenediamine, tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, and 4,4 ′. -Diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 1,4-bis [ 1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, bis (2-dimethylaminoethyl) ether, bis ( 2-diethylaminoethyl) ether, 1- (2-hydroxyethyl) 2-imidazolidinone, 2-quinoxalinium linoleic, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, and the like.

  Examples of the (cyclo) alkylamine compound having three or more nitrogen atoms include polymers such as polyethyleneimine, polyallylamine, and 2-dimethylaminoethylacrylamide.

  Examples of the nitrogen-containing heterocyclic compound include nitrogen-containing aromatic heterocyclic compounds and nitrogen-containing aliphatic heterocyclic compounds.

  Examples of the nitrogen-containing aromatic heterocyclic compound include imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2. -Imidazoles such as methyl-1H-imidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenyl Examples thereof include pyridines such as pyridine, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine, 2,2 ′: 6 ′, 2 ″ -terpyridine.

  Examples of the nitrogen-containing aliphatic heterocyclic compound include piperazine such as piperazine and 1- (2-hydroxyethyl) piperazine; pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, proline, piperidine, piperidine ethanol, 3-piperidino- 1,2-propanediol, morpholine, 4-methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetylmorpholine, 3- (N-morpholino) -1,2-propanediol, 1,4-dimethylpiperazine, Examples include 1,4-diazabicyclo [2.2.2] octane.

  Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt-butoxy. Carbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-2-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, (S)-(- ) -1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, (R)-(+)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, Nt-butoxycarbonyl-4-hydroxypiperidine, Nt-butoxycarbonylpyrrolidine, Nt-butoxycarbonylpyrrolidine Razine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4′- Diaminodiphenylmethane, N, N′-di-t-butoxycarbonylhexamethylenediamine, N, N, N ′, N′-tetra-t-butoxycarbonylhexamethylenediamine, N, N′-di-t-butoxycarbonyl- 1,7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8-diaminooctane, N, N′-di-t-butoxycarbonyl-1,9-diaminononane, N, N′-di -T-butoxycarbonyl-1,10-diaminodecane, N, N'-di-t-butoxycarbonyl-1,12-diaminododecane, N, N -Di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole Nt-butoxycarbonyl group-containing amino compounds such as formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N- Examples include methylpyrrolidone, N-acetyl-1-adamantylamine, and isocyanuric acid tris (2-hydroxyethyl).

  Examples of urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, and the like.

The content of the basic compound (preferably a nitrogen-containing compound) in the treatment liquid is not particularly limited, but is preferably 10% by mass or less with respect to the total amount of the treatment liquid in terms of more excellent effects of the present invention. 5-5 mass% is preferable.
In the present invention, the above nitrogen-containing compounds may be used alone or in combination of two or more having different chemical structures.

The above-described treatment liquid can be suitably applied to non-chemical amplification resists for the purpose of solving the same problems as in the present application.
Examples of non-chemical amplification resists include the following.
(1) Resist materials whose solubility changes when the main chain is cleaved by irradiation with g-line, h-line, i-line, KrF, ArF, EB, EUV or the like, and the molecular weight is reduced (for example, JP 2013-210411 A) The main component is a copolymer of an α-chloroacrylate ester compound and an α-methylstyrene compound described in paragraphs 0025 to 0029 and 0056 of the publication and paragraphs 0032 to 0036 and 0063 of US Patent Publication 2015/0008211. Resist material, etc.).
(2) Resist materials such as hydrogen silsesquioxane (HSQ) accompanied by silanol condensation reaction caused by g-line, h-line, i-line, KrF, ArF, EB or EUV, chlorine-substituted calixarene, etc. (3) g Metal complexes that absorb light such as wire, h-line, i-line, KrF, ArF, EB or EUV (magnesium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, indium, tin , Antimony, cesium, zirconium, hafnium, etc., including titanium, zirconium, and hafnium, which are preferable from the viewpoint of pattern formation), and ligand exchange process in combination with ligand elimination and photoacid generator (Japanese Patent Laid-Open No. 2015-075500, paragraphs 0017 to 0033, 0037 to 0047, JP 2012-185) 85 No. paragraphs 0017～0032,0043～0044 resist material described in U.S. paragraph 0042～0051,0066 such patent publications 2012/0208125) and the like.

Further, the above-described processing liquid can be suitably applied to a silicon-based resist for the purpose of solving the same problems as in the present application.
Examples of the silicon-based resist include resist materials described in paragraphs 0010 to 0062 and paragraphs 0129 to 0165 described in JP 2008-83384 A.

[Pattern formation method]
The pattern forming method of the present invention includes a resist film forming step of forming a resist film using an actinic ray-sensitive or radiation-sensitive composition (hereinafter also referred to as “resist composition”), and an exposure step of exposing the resist film. And a processing step of processing the exposed resist film with the processing liquid described above.
According to the pattern forming method of the present invention, since the above-described processing liquid is used, the occurrence of pattern collapse in the resist L / S pattern and the occurrence of defective omission in the resist C / H pattern can be suppressed at the same time.

  Hereinafter, each process which the pattern formation method of this invention has is demonstrated. As an example of the processing step, each of the development step and the rinsing step will be described.

<Resist film formation step (a)>
The resist film forming step is a step of forming a resist film using an actinic ray-sensitive or radiation-sensitive composition, and can be performed, for example, by the following method.
In order to form a resist film (actinic ray-sensitive or radiation-sensitive composition film) on a substrate using an actinic ray-sensitive or radiation-sensitive composition, each component described later is dissolved in a solvent and activated. A light-sensitive or radiation-sensitive composition is prepared, filtered as necessary, and then applied onto a substrate. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon having a pore size of 0.1 microns or less, more preferably 0.05 microns or less, and still more preferably 0.03 microns or less.

  The actinic ray-sensitive or radiation-sensitive composition is applied to a substrate (for example, silicon or silicon dioxide coating) used for manufacturing an integrated circuit element by an appropriate application method such as a spinner. Thereafter, it is dried to form a resist film. If necessary, various base films (inorganic films, organic films, antireflection films) may be formed under the resist film.

As a drying method, a method of heating and drying is generally used. Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
The heating temperature is preferably 80 to 180 ° C, more preferably 80 to 150 ° C, still more preferably 80 to 140 ° C, and particularly preferably 80 to 130 ° C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and still more preferably 60 to 600 seconds.

The film thickness of the resist film is generally 200 nm or less, preferably 100 nm or less.
For example, in order to resolve a 1: 1 line and space pattern having a size of 30 nm or less, the thickness of the formed resist film is preferably 50 nm or less. If the film thickness is 50 nm or less, pattern collapse is less likely to occur when a development process described later is applied, and better resolution performance is obtained.
More preferably, the film thickness ranges from 15 nm to 45 nm. If the film thickness is 15 nm or more, sufficient etching resistance can be obtained. More preferably, the film thickness ranges from 15 nm to 40 nm. When the film thickness is within this range, etching resistance and better resolution performance can be satisfied at the same time.

  In the pattern forming method of the present invention, an upper layer film (top coat film) may be formed on the resist film. The upper film can be formed using, for example, an upper film forming composition containing a hydrophobic resin, an acid generator, and a basic compound. The upper layer film and the composition for forming the upper layer film are as described below.

<Exposure step (b)>
An exposure process is a process of exposing the said resist film, for example, can be performed with the following method.
The resist film formed as described above is irradiated with actinic rays or radiation through a predetermined mask. Note that in electron beam irradiation, drawing (direct drawing) without using a mask is common. In addition, it is also preferable to include a pre-exposure bake step (also referred to as a post-application bake step (PB; Prebake)) after film formation and before the exposure step.
Although it does not specifically limit as actinic light or a radiation, For example, they are a KrF excimer laser, an ArF excimer laser, EUV light, an electron beam (EB) etc. The exposure may be immersion exposure.

<Bake>
In the pattern formation method of this invention, it is also preferable to include a post-exposure bake process (PEB; Post Exposure Bake) after the exposure process and before the development process. The post-exposure baking process promotes the reaction of the exposed area, and the sensitivity and pattern shape are improved.
The heating temperature is preferably 80 to 150 ° C, more preferably 80 to 140 ° C, and still more preferably 80 to 130 ° C.
The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and still more preferably 60 to 600 seconds.
Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
The heating temperature and heating time in the pre-exposure baking process are the same as the heating temperature and heating time in the post-exposure baking process.

<Process (c) for processing exposed film>
<< Development process >>
The development step is a step of developing the exposed resist film with a developer.

As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied.
Moreover, you may implement the process of stopping image development, after the process of developing, substituting with another solvent.
The development time is not particularly limited as long as the resin in the unexposed area is sufficiently dissolved, and is usually 10 to 300 seconds, preferably 20 to 120 seconds.
The temperature of the developer is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.

  As the developer used in the development step, it is preferable to use the above-described processing solution. The developer is as described above. In addition to development using a processing solution, development with an alkaline developer may be performed (so-called double development).

<< Rinse process >>
The rinsing step is a step of washing (rinsing) with a rinsing liquid after the developing step.

In the rinsing step, the developed wafer is cleaned using the rinsing liquid.
The method of the cleaning process is not particularly limited. For example, a method of continuously discharging the rinse liquid onto the substrate rotating at a constant speed (rotary discharge method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid on the substrate surface (spray method), and the like can be applied. Among these, a cleaning process is performed by a rotary discharge method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate.
The rinse time is not particularly limited, but is usually 10 seconds to 300 seconds, preferably 10 seconds to 180 seconds, and most preferably 20 seconds to 120 seconds.
The temperature of the rinse liquid is preferably 0 to 50 ° C, and more preferably 15 to 35 ° C.

In addition, after the developing process or the rinsing process, a process of removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.
Furthermore, after the development process or the rinse process or the process with the supercritical fluid, a heat treatment can be performed in order to remove the solvent remaining in the pattern. The heating temperature is not particularly limited as long as a good resist pattern can be obtained, and is usually 40 to 160 ° C. The heating temperature is preferably 50 to 150 ° C, and most preferably 50 to 110 ° C. The heating time is not particularly limited as long as a good resist pattern can be obtained, but is usually 15 to 300 seconds, and preferably 15 to 180 seconds.

  In the pattern forming method of the present invention, at least one of the developer and the rinsing liquid is the above-described processing liquid, and it is particularly preferable that the rinsing liquid is the above-described processing liquid.

In general, the developer and the rinse liquid are stored in a waste liquid tank through a pipe after use. At that time, for example, when using an ester solvent as a developer and a hydrocarbon solvent as a rinse liquid, a resist dissolved in the developer is deposited, and adheres to a wafer side rear surface, a pipe side surface, Dirty equipment.
In order to solve the above problem, there is a method in which a solvent in which the resist is dissolved is again passed through the pipe. As a method of passing through the piping, after washing with a rinsing liquid, cleaning the back and side surfaces of the substrate with a solvent that dissolves the resist, or passing the solvent through which the resist dissolves without contacting the resist. The method of flowing is mentioned.
The solvent passed through the pipe is not particularly limited as long as it can dissolve the resist, and examples thereof include the organic solvents used as the developer described above. Specifically, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate , Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol mono Chirueteru, 2-heptanone, ethyl lactate, 1-propanol, and acetone. Among these, PGMEA, PGME, and cyclohexanone are preferable.

[Actinic ray or radiation sensitive composition (resist composition)]
Next, the actinic ray-sensitive or radiation-sensitive composition that is preferably used in combination with the treatment liquid of the present invention will be described in detail.

(A) Resin <Resin (A)>
The actinic ray-sensitive or radiation-sensitive composition preferably used in combination with the treatment liquid of the present invention preferably contains a resin (A). The resin (A) is preferably a resin having a group that decomposes by the action of an acid to generate a polar group. At least (i) a repeating unit having a group that decomposes by the action of an acid to generate a carboxyl group (further Or a repeating unit having a phenolic hydroxyl group) or at least (ii) a repeating unit having a phenolic hydroxyl group.
In addition, when it has the repeating unit which decomposes | disassembles by the effect | action of an acid and has a carboxyl group, the solubility with respect to an alkali developing solution will increase by the effect | action of an acid, and the solubility with respect to an organic solvent will decrease.

  As a repeating unit which has phenolic hydroxyl group which resin (A) has, the repeating unit represented by the following general formula (I) is mentioned, for example.

In the formula, R ₄₁ , R ₄₂ and R ₄₃ each independently represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₄₂ may form a ring with Ar _4, R ₄₂ in this case represents a single bond or an alkylene group.
X ₄ represents a single bond, —COO—, or —CONR ₆₄ —, and R ₆₄ represents a hydrogen atom or an alkyl group.
L ₄ represents a single bond or an alkylene group.
Ar ₄ represents an (n + 1) -valent aromatic ring group, and when bonded to R ₄₂ to form a ring, represents an (n + 2) -valent aromatic ring group.
n represents an integer of 1 to 5.

As the alkyl group for R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I), a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec- Examples thereof include alkyl groups having 20 or less carbon atoms such as butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group, more preferably alkyl groups having 8 or less carbon atoms, particularly preferably alkyl groups having 3 or less carbon atoms. Can be mentioned.

The alkyl group of R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I) may be cyclic and may be monocyclic or polycyclic. When the alkyl group of R ₄₁ , R ₄₂ , and R ₄₃ is cyclic, it is preferably a monocyclic type having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group, which may have a substituent. A cycloalkyl group is mentioned.
Examples of the halogen atom of R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.
As the alkyl group contained in the alkoxycarbonyl group of R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I), the same alkyl groups as those described above for R ₄₁ , R ₄₂ and R ₄₃ are preferable.

  Preferred substituents in each of the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyls. Groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, nitro groups and the like, and the substituent preferably has 8 or less carbon atoms.

Ar ₄ represents an (n + 1) -valent aromatic ring group. The divalent aromatic ring group when n is 1 is, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, or an anthracenylene group, or, for example, thiophene, furan, pyrrole, benzo Preferable examples include aromatic ring groups containing a heterocycle such as thiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole. These may further have a substituent.

Specific examples of the (n + 1) -valent aromatic ring group in the case where n is an integer of 2 or more include (n-1) arbitrary hydrogen atoms removed from the above-described specific examples of the divalent aromatic ring group. The group formed can be preferably mentioned.
The (n + 1) -valent aromatic ring group may further have a substituent.

Examples of the substituent that the above-described alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n + 1) -valent aromatic ring group may have include R ₄₁ , R ₄₂ , and R ₄₃ in formula (I). Examples include alkyl groups such as alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, and butoxy groups; aryl groups such as phenyl groups; and the like.
_-CONR 64 represented by X ₄ - _{(R 64} represents a hydrogen atom, an alkyl group) The alkyl group for _{R 64} in, preferably an optionally substituted methyl group, an ethyl group, a propyl group , An isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a dodecyl group, or the like, and an alkyl group having a carbon number of 8 or less is more preferable. Can be mentioned.
X ₄ is preferably a single bond, —COO—, or —CONH—, and more preferably a single bond or —COO—.

The alkylene group for L ₄ is preferably an alkylene group having 1 to 8 carbon atoms, such as an optionally substituted methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group.
As Ar ₄ , an aromatic ring group having 6 to 18 carbon atoms which may have a substituent is more preferable, and a benzene ring group, a naphthalene ring group, and a biphenylene ring group are particularly preferable.
The repeating unit represented by the general formula (I) preferably has a hydroxystyrene structure. That is, Ar ₄ is preferably a benzene ring group.

  The repeating unit having a phenolic hydroxyl group contained in the resin (A) is preferably a repeating unit represented by the following general formula (p1).

  R in the general formula (p1) represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different. As R in the general formula (p1), a hydrogen atom is particularly preferable.

  Ar in the general formula (p1) represents an aromatic ring, for example, an aromatic carbon which may have a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, a phenanthrene ring, or the like. A hydrogen ring or a heterocycle such as a thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, thiazole ring, etc. Examples thereof include aromatic heterocycles. Of these, a benzene ring is most preferable.

  M in the general formula (p1) represents an integer of 1 to 5, and is preferably 1.

  Hereinafter, although the specific example of the repeating unit which has the phenolic hydroxyl group which resin (A) has is shown, this invention is not limited to this. In the formula, a represents 1 or 2.

  The content of the repeating unit having a phenolic hydroxyl group is preferably from 0 to 50 mol%, more preferably from 0 to 45 mol%, still more preferably from 0 to 40 mol%, based on all repeating units in the resin (A). is there.

  The repeating unit having a group that decomposes by the action of an acid and generates a carboxyl group in the resin (A) is a repeating unit having a group in which a hydrogen atom of the carboxyl group is substituted with a group that decomposes and leaves by the action of an acid It is.

Examples of the group capable of leaving by the action of an acid _{include, -C (R 36) (R} 37) (R 38), - C (R 36) (R 37) (OR 39), - C (R 01) (R 02 ) (OR ₃₉ ) and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R ₀₁ and R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

  As the repeating unit having a group capable of decomposing by the action of an acid to generate a carboxyl group, the resin (A) is preferably a repeating unit represented by the following general formula (AI).

In General Formula (AI), Xa ₁ represents a hydrogen atom or an alkyl group which may have a substituent.
T represents a single bond or a divalent linking group.
Rx _{1 to} Rx ₃ each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic). However, when all of Rx _{1 to} Rx ₃ are alkyl groups (straight or branched), at least two of Rx _{1 to} Rx ₃ are preferably methyl groups.
Two of Rx _{1 to} Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the alkyl group which may have a substituent represented by Xa ₁ include a group represented by a methyl group or —CH ₂ —R ₁₁ . R ₁₁ represents a halogen atom (such as a fluorine atom), a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably 3 or less carbon atoms. And more preferably a methyl group. In one embodiment, Xa ₁ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, a hydroxymethyl group, or the like.
Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a —COO—Rt— group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group, — (CH ₂ ) ₂ — group, or — (CH ₂ ) ₃ — group.

Examples of the alkyl group rx ₁ to Rx _3, methyl, ethyl, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, those having 1 to 4 carbon atoms such as t- butyl group.
Examples of the cycloalkyl group represented by Rx _{1 to} Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Groups are preferred.
Examples of the cycloalkyl group formed by combining two of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group A polycyclic cycloalkyl group such as a group is preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.
The cycloalkyl group formed by combining two of Rx _{1 to} Rx ₃ is, for example, a group in which one of the methylene groups constituting the ring has a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. It may be replaced.
The repeating unit represented by the general formula (AI) preferably has, for example, an embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-described cycloalkyl group.

  Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxy group. A carbonyl group (C2-C6) etc. are mentioned, C8 or less is preferable.

The repeating unit represented by formula (AI) is preferably an acid-decomposable (meth) acrylic acid tertiary alkyl ester-based repeating unit (Xa ₁ represents a hydrogen atom or a methyl group, and T is a single bond. Is a repeating unit). Repeat More preferably, independently is Rx ₁ to Rx ₃ each a repeating unit represents a linear or branched alkyl group, more preferably, the independently is Rx ₁ to Rx ₃ each represent a linear alkyl group Unit.

Although the specific example of the repeating unit which has the group which decomposes | disassembles by the effect | action of an acid and has a carboxyl group which the resin (A) has is shown below, this invention is not limited to this.
In specific examples, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when there are a plurality of them, each is independent. p represents 0 or a positive integer. Examples of the substituent containing a polar group represented by Z include a linear or branched alkyl group having a hydroxyl group, a cyano group, an amino group, an alkylamide group, or a sulfonamide group, and a cycloalkyl group. Is an alkyl group having a hydroxyl group. As the branched alkyl group, an isopropyl group is particularly preferable.

  The content of the repeating unit having a group capable of decomposing by the action of an acid to generate a carboxyl group is preferably from 15 to 90 mol%, more preferably from 20 to 90 mol%, based on all repeating units in the resin (A). 25-80 mol% is still more preferable, and 30-70 mol% is still more preferable.

The resin (A) preferably further contains a repeating unit having a lactone group.
As the lactone group, any group can be used as long as it contains a lactone structure, but it is preferably a group containing a 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed to form a spiro structure are preferred.
It is more preferable to have a repeating unit having a group having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-16). Further, a group having a lactone structure may be directly bonded to the main chain. Preferred lactone structures are groups represented by general formulas (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14).

The lactone structure moiety may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of Rb ₂ may be the same or different, and a plurality of Rb ₂ may be bonded to form a ring.

  Examples of the repeating unit having a group having a lactone structure represented by any of the general formulas (LC1-1) to (LC1-16) include a repeating unit represented by the following general formula (AI). Can do.

In General Formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
Preferred substituents that the alkyl group represented by Rb ₀ may have include a hydroxyl group and a halogen atom.
Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ is preferably a hydrogen atom or a methyl group.
Ab is a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these. Represent. A linking group represented by a single bond or —Ab ₁ —CO ₂ — is preferable. Ab ₁ is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.
V represents a group represented by any one of the general formulas (LC1-1) to (LC1-16).

  The repeating unit having a group having a lactone structure usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more.

Specific examples of the repeating unit having a group having a lactone structure are given below, but the present invention is not limited thereto. In the formula, Rx represents a hydrogen atom, —CH ₃ group, —CH ₂ OH group or —CF ₃ group.

The content of the repeating unit having a lactone group is preferably from 1 to 65 mol%, more preferably from 1 to 30 mol%, still more preferably from 5 to 25 mol%, based on all repeating units in the resin (A). Even more preferred is ˜20 mol%.
The resin (A) can further have a repeating unit containing an organic group having a polar group, particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group.
This improves the substrate adhesion and developer compatibility. The alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group, a diamantyl group, or a norbornane group. The polar group is preferably a hydroxyl group or a cyano group.
Specific examples of the repeating unit having a polar group are listed below, but the present invention is not limited thereto.

  When the resin (A) has a repeating unit containing an organic group having a polar group, the content thereof is preferably 1 to 50 mol%, preferably 1 to 30 mol based on all repeating units in the resin (A). % Is more preferable, 5 to 25 mol% is more preferable, and 5 to 20 mol% is still more preferable.

Furthermore, as a repeating unit other than the above, a repeating unit having a group capable of generating an acid (photoacid generating group) upon irradiation with actinic rays or radiation can also be included. In this case, it can be considered that the repeating unit having this photoacid-generating group corresponds to the compound (B) that generates an acid upon irradiation with actinic rays or radiation described later.
Examples of such a repeating unit include a repeating unit represented by the following general formula (4).

R ⁴¹ represents a hydrogen atom or a methyl group. L ⁴¹ represents a single bond or a divalent linking group. L ⁴² represents a divalent linking group. W represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.

  Although the specific example of the repeating unit represented by General formula (4) below is shown, this invention is not limited to this.

  In addition, examples of the repeating unit represented by the general formula (4) include the repeating units described in paragraphs <0094> to <0105> of JP-A No. 2014-041327.

  When the resin (A) contains a repeating unit having a photoacid-generating group, the content of the repeating unit having a photoacid-generating group is preferably 1 to 40 mol% with respect to all repeating units in the resin (A). More preferably, it is 5-35 mol%, More preferably, it is 5-30 mol%.

Resin (A) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable.
Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate; amide solvents such as dimethylformamide and dimethylacetamide; And a solvent that dissolves an actinic ray-sensitive or radiation-sensitive composition such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone. More preferably, the polymerization is performed using the same solvent as that used in the actinic ray-sensitive or radiation-sensitive composition. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The density | concentration of a reaction material is 5-50 mass%, Preferably it is 10-30 mass%.
The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 60 ° C to 100 ° C.
Purification can be accomplished by using a liquid-liquid extraction method that removes residual monomers and oligomer components by washing with water or an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. In a solid state such as reprecipitation method by removing the residual monomer by coagulating the resin in the poor solvent by dropping the resin solution into the poor solvent, or washing the filtered resin slurry with the poor solvent Ordinary methods such as the purification method can be applied.

The weight average molecular weight of the resin (A) is preferably from 1,000 to 200,000, more preferably from 3,000 to 20,000, and most preferably from 5,000 to 15, as a polystyrene-converted value by the GPC method. 000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.
Another particularly preferable form of the weight average molecular weight of the resin (A) is 3,000 to 9,500 in terms of polystyrene by GPC method. By setting the weight average molecular weight to 3,000 to 9,500, resist residues (hereinafter also referred to as “scum”) are particularly suppressed, and a better pattern can be formed.
The degree of dispersion (molecular weight distribution) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, particularly preferably 1.2 to 2.0. . The smaller the degree of dispersion, the better the resolution and the resist shape, the smoother the side wall of the resist pattern, and the better the roughness.

In the actinic ray-sensitive or radiation-sensitive composition, the content of the resin (A) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total solid content.
In the actinic ray-sensitive or radiation-sensitive composition, the resin (A) may be used alone or in combination.

  Moreover, resin (A) may contain the repeating unit represented by the following general formula (VI).

In general formula (VI), R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R ₆₂ may be bonded to Ar ₆ to form a ring, and R ₆₂ in this case represents a single bond or an alkylene group.
X ₆ represents a single bond, —COO—, or —CONR ₆₄ —. R ₆₄ represents a hydrogen atom or an alkyl group.
L ₆ represents a single bond or an alkylene group.
Ar ₆ represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when bonded to R ₆₂ to form a ring.
Y ₂ independently represents a hydrogen atom or a group capable of leaving by the action of an acid when n ≧ 2. However, at least one of Y ₂ represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4.
As the group Y ₂ leaving by the action of an acid, a structure represented by the following general formula (VI-A) is more preferable.

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined.
M represents a single bond or a divalent linking group.
Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group.
At least two of Q, M, and L ₁ may combine to form a ring (preferably a 5-membered or 6-membered ring).

  The repeating unit represented by the general formula (VI) is preferably a repeating unit represented by the following general formula (3).

In the general formula (3), Ar ₃ represents an aromatic ring group.
R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, or a heterocyclic group.
M ₃ represents a single bond or a divalent linking group.
Q ₃ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.
At least two of Q ₃ , M ₃ and R ₃ may be bonded to form a ring.

The aromatic ring group represented by Ar ₃ is the same as Ar ₆ in the general formula (VI) when n in the general formula (VI) is 1, more preferably a phenylene group or a naphthylene group, A phenylene group is preferred.

  Specific examples of the repeating unit represented by the general formula (VI) are shown below, but the present invention is not limited thereto.

  The resin (A) also preferably contains a repeating unit represented by the following general formula (4).

In the general formula (4), R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ may be bonded to L ₄ to form a ring, and R ₄₂ in this case represents an alkylene group.
L ₄ represents a single bond or a divalent linking group, and in the case of forming a ring with R ₄₂ , represents a trivalent linking group.
R ₄₄ and R ₄₅ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, or a heterocyclic group.
M ₄ represents a single bond or a divalent linking group.
Q ₄ represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.
At least two of Q ₄ , M ₄ and R ₄₄ may be bonded to form a ring.
R ₄₁ , R ₄₂ and R ₄₃ have the same meanings as R ₅₁ , R ₅₂ and R _{53 in} the general formula (V), and preferred ranges are also the same.
L ₄ has the same meaning as L _{5 in} the general formula (V), and the preferred range is also the same.
R ₄₄ and R ₄₅ have the same meaning as R _{3 in} the general formula (3), and the preferred range is also the same.
M ₄ has the same meaning as M _{3 in} the general formula (3), and the preferred range is also the same.
Q ₄ has the same meaning as Q _{3 in} the general formula (3), and the preferred range is also the same.
Examples of the ring formed by combining at least two of Q ₄ , M ₄ and R ₄₄ include rings formed by combining at least two of Q ₃ , M ₃ and R ₃ , and the preferred range is the same. It is.
Specific examples of the repeating unit represented by the general formula (4) are shown below, but the present invention is not limited thereto.

  Moreover, resin (A) may contain the repeating unit represented by the following general formula (BZ).

In general formula (BZ), AR represents an aryl group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and AR may be bonded to each other to form a non-aromatic ring.
R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkyloxycarbonyl group.

  Specific examples of the repeating unit represented by the general formula (BZ) are shown below, but are not limited thereto.

  One type of repeating unit having the acid-decomposable group may be used, or two or more types may be used in combination.

  The content of the repeating unit having an acid-decomposable group in the resin (A) (when there are a plurality of types) is 5 mol% or more and 80 mol% or less with respect to all the repeating units in the resin (A). It is preferably 5 mol% or more and 75 mol% or less, more preferably 10 mol% or more and 65 mol% or less.

  Resin (A) may contain the repeating unit represented by the following general formula (V) or the following general formula (VI).

In the formula, R ₆ and R ₇ are each independently a hydrogen atom, a hydroxy group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group or an acyloxy group, a cyano group, a nitro group, An amino group, a halogen atom, an ester group (-OCOR or -COOR: R represents an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group.
n ₃ represents an integer of 0 to 6.
n ₄ represents an integer of 0-4.
X ⁴ is a methylene group, an oxygen atom or a sulfur atom.
Although the specific example of the repeating unit represented by general formula (V) or general formula (VI) is shown below, it is not limited to these.

  The resin (A) may further have a repeating unit having a silicon atom in the side chain. Examples of the repeating unit having a silicon atom in the side chain include a (meth) acrylate-based repeating unit having a silicon atom and a vinyl-based repeating unit having a silicon atom. The repeating unit having a silicon atom in the side chain is typically a repeating unit having a group having a silicon atom in the side chain. Examples of the group having a silicon atom include a trimethylsilyl group, a triethylsilyl group, and triphenyl. Silyl group, tricyclohexylsilyl group, tristrimethylsiloxysilyl group, tristrimethylsilylsilyl group, methylbistrimethylsilylsilyl group, methylbistrimethylsiloxysilyl group, dimethyltrimethylsilylsilyl group, dimethyltrimethylsiloxysilyl group, or cyclic or Examples include linear polysiloxanes, cage-type, ladder-type or random-type silsesquioxane structures. In the formula, R and R1 each independently represent a monovalent substituent. * Represents a bond.

  Suitable examples of the repeating unit having the above group include a repeating unit derived from an acrylate or methacrylate compound having the above group, and a repeating unit derived from a compound having the above group and a vinyl group.

The repeating unit having a silicon atom is preferably a repeating unit having a silsesquioxane structure, whereby it is ultrafine (for example, a line width of 50 nm or less), and the cross-sectional shape has a high aspect ratio (for example, In the formation of a pattern having a film thickness / line width of 3 or more, a very excellent collapse performance can be exhibited.
Examples of the silsesquioxane structure include a cage-type silsesquioxane structure, a ladder-type silsesquioxane structure (ladder-type silsesquioxane structure), a random-type silsesquioxane structure, and the like. Of these, a cage-type silsesquioxane structure is preferable.
Here, the cage silsesquioxane structure is a silsesquioxane structure having a cage structure. The cage silsesquioxane structure may be a complete cage silsesquioxane structure or an incomplete cage silsesquioxane structure, but may be a complete cage silsesquioxane structure. preferable.
The ladder-type silsesquioxane structure is a silsesquioxane structure having a ladder-like skeleton.
The random silsesquioxane structure is a silsesquioxane structure having a random skeleton.

  The cage silsesquioxane structure is preferably a siloxane structure represented by the following formula (S).

In the above formula (S), R represents a monovalent organic group. A plurality of R may be the same or different.
The organic group is not particularly limited, and specific examples include a hydroxy group, a nitro group, a carboxy group, an alkoxy group, an amino group, a mercapto group, a blocked mercapto group (for example, a mercapto group blocked (protected) with an acyl group) ), An acyl group, an imide group, a phosphino group, a phosphinyl group, a silyl group, a vinyl group, a hydrocarbon group optionally having a hetero atom, a (meth) acryl group-containing group, and an epoxy group-containing group.
Examples of the hetero atom of the hydrocarbon group that may have a hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom.
Examples of the hydrocarbon group of the hydrocarbon group that may have a hetero atom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group obtained by combining these.
The aliphatic hydrocarbon group may be linear, branched or cyclic. Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (particularly having 1 to 30 carbon atoms), a linear or branched alkenyl group (particularly having 2 to 30 carbon atoms), Examples thereof include a linear or branched alkynyl group (particularly having 2 to 30 carbon atoms).
As said aromatic hydrocarbon group, C6-C18 aromatic hydrocarbon groups, such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned, for example.

  When resin (A) has the repeating unit which has a silicon atom in the said side chain, the content is preferable with respect to all the repeating units in resin (A), 1-30 mol%, 5-25 mol% Is more preferably 5 to 20 mol%.

(B) Compound that generates acid by actinic ray or radiation (photoacid generator)
The actinic ray-sensitive or radiation-sensitive resin composition preferably contains a compound that generates an acid by actinic rays or radiation (hereinafter also referred to as “photo acid generator << PAG: Photo Acid Generator”).
The photoacid generator may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Moreover, you may use together the form incorporated in a part of polymer and the form of a low molecular compound.
When the photoacid generator is in the form of a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
When the photoacid generator is in a form incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) or in a resin different from the resin (A).
In the present invention, the photoacid generator is preferably in the form of a low molecular compound.
The photoacid generator is not particularly limited as long as it is a known one, but upon irradiation with actinic rays or radiation, preferably electron beams or extreme ultraviolet rays, an organic acid such as sulfonic acid, bis (alkylsulfonyl) imide, or Compounds that generate at least one of tris (alkylsulfonyl) methides are preferred.
More preferred examples include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).

In the general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).
Z ⁻ represents a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).

  Non-nucleophilic anions include, for example, sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphor sulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyls). Carboxylate anion, etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.

  The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. 3-30 cycloalkyl groups are mentioned.

  The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group.

The alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7), an alkylthio group (preferably 1 to 15 carbon atoms), an alkylsulfonyl group (preferably 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably 1 to 15 carbon atoms), an aryloxysulfonyl group (preferably carbon) Formula 6-20), alkylaryloxysulfonyl group (preferably C7-20), cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. .
About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

  The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

  Examples of the sulfonylimide anion include saccharin anion.

The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. A fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
The alkyl groups in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure. This increases the acid strength.

Examples of other non-nucleophilic anions include fluorinated phosphorus (eg, PF ₆ ⁻ ), fluorinated boron (eg, BF ₄ ⁻ ), and fluorinated antimony (eg, SbF ₆ ⁻ ). .

  Examples of the non-nucleophilic anion include an aliphatic sulfonate anion in which at least α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group having a fluorine atom And a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom. More preferably, the non-nucleophilic anion is a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, perfluoro An octane sulfonate anion, a pentafluorobenzene sulfonate anion, and a 3,5-bis (trifluoromethyl) benzene sulfonate anion.

  From the viewpoint of acid strength, the pKa of the generated acid is preferably −1 or less in order to improve sensitivity.

  Moreover, as a non-nucleophilic anion, the anion represented with the following general formula (AN1) is also mentioned as a preferable aspect.

In the formula, each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are a plurality of R ¹ and R ² , they may be the same or different.
L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
A represents a cyclic organic group.
x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

The general formula (AN1) will be described in more detail.
The alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F ₉ may be mentioned, among which a fluorine atom and CF ₃ are preferable.
In particular, it is preferable that both Xf are fluorine atoms.

The alkyl group of R ¹ and R ² may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferably, it is a C1-C4 perfluoroalkyl group. Specific examples of the alkyl group having a substituent for R ¹ and R ² include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , and C ₇ F _{15. , C 8 F 17, CH 2} CF 3, CH 2 CH 2 CF 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F ₉ can be mentioned, among which CF ₃ is preferable.
R ¹ and R ² are preferably a fluorine atom or CF ₃ .

x is preferably 1 to 10, and more preferably 1 to 5.
y is preferably 0 to 4, and more preferably 0.
z is preferably 0 to 5, and more preferably 0 to 3.
The divalent linking group of L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group, a cycloalkylene group, An alkenylene group or a linking group in which a plurality of these groups are linked can be exemplified, and a linking group having a total carbon number of 12 or less is preferred. Among these, —COO—, —OCO—, —CO—, and —O— are preferable, and —COO— and —OCO— are more preferable.

In the general formula (AN1), as a combination of partial structures other than A, SO ³ —CF ₂ —CH ₂ —OCO—, SO ³ —CF ₂ —CHF—CH ₂ —OCO—, SO ³ —CF _{^{2 -COO-, SO 3- -CF 2 -CF}} 2 -CH 2 -, SO 3- -CF 2 -CH (CF 3) -OCO- are mentioned as preferred.

The cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and is not limited to alicyclic groups, aryl groups, and heterocyclic groups (not only those having aromaticity but also aromaticity). And the like).
The alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, or a tetracyclododecane group. A polycyclic cycloalkyl group such as a nyl group and an adamantyl group is preferred. Among them, an alicyclic group having a bulky structure having 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, or the like is present in the film in the post-exposure heating step. It is preferable from the viewpoint of improving diffusibility and improving MEEF (mask error enhancement factor).
Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.
Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, those derived from a furan ring, a thiophene ring and a pyridine ring are preferred.

  Examples of the cyclic organic group include lactone structures, and specific examples include lactone structures represented by the following general formulas (LC1-1) to (LC1-17).

The cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be linear, branched or cyclic, preferably 1 to 12 carbon atoms), cyclo Alkyl group (which may be monocyclic, polycyclic or spirocyclic, preferably 3 to 20 carbon atoms), aryl group (preferably 6 to 14 carbon atoms), hydroxy group, alkoxy group, ester group, amide Group, urethane group, ureido group, thioether group, sulfonamide group, sulfonic acid ester group and the like. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.
Incidentally, the above substituents, in the above (LC1-1) ~ (LC1-17) corresponding to Rb _2. Moreover, in said (LC1-1)-(LC1-17), n2 represents the integer of 0-4. When n2 is 2 or more, a plurality of Rb ₂ may be the same or different, and a plurality of Rb ₂ may be bonded to form a ring.

In General Formula (ZI), examples of the organic group represented by R ₂₀₁ , R _202, and R ₂₀₃ include an aryl group, an alkyl group, and a cycloalkyl group.
Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , at least one is preferably an aryl group, more preferably all three are aryl groups. As the aryl group, in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can be used. Preferred examples of the alkyl group and cycloalkyl group represented by R _{201 to} R ₂₀₃ include a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. More preferable examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. More preferable examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. These groups may further have a substituent. Further, the substituents that may be present include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably Has 3 to 15 carbon atoms, an aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group ( Preferable examples thereof include 2 to 7 carbon atoms, but are not limited thereto.

Next, general formulas (ZII) and (ZIII) will be described.
In the general formulas (ZII) and (ZIII), R _{204 to} R ₂₀₇ each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
The aryl group for R _{204 to} R ₂₀₇ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group of R _{204 to} R ₂₀₇ may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group in R _{204 to} R ₂₀₇ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).

The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may have a substituent. Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may have include, for example, an alkyl group (eg, having 1 to 15 carbon atoms) and a cycloalkyl group (eg, having 3 to 15 carbon atoms). ), An aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.

In general formula (ZII), Z ⁻ represents a non-nucleophilic anion. Specifically, it is the same as that described as Z ⁻ in the general formula (ZI), and the preferred form is also the same.

  Specific examples of general formulas (ZI) to (ZIII) are shown below, but are not limited thereto.

In the present invention, the photoacid generator has a volume of 130 to ³ or more by irradiation with an electron beam or extreme ultraviolet rays from the viewpoint of suppressing the diffusion of the acid generated by exposure to the non-exposed portion and improving the resolution. (more preferably sulfonic acid) in the size of the acid is a compound which generates, more preferably (more preferably sulfonic acid) acid volume 190 Å ³ or more in size is a compound that generates a volume 270 Å ³ More preferably, the compound generates an acid having a size as described above (more preferably sulfonic acid), and particularly preferably a compound that generates an acid having a volume of 400 ³ or more (more preferably sulfonic acid). . However, from the viewpoint of sensitivity and coating solvent solubility, the volume is preferably 2000 ³ or less, and more preferably 1500 ³ or less. The volume value was determined using “WinMOPAC” manufactured by Fujitsu Limited. That is, first, the chemical structure of the acid according to each example is input, and then the most stable conformation of each acid is determined by molecular force field calculation using the MM3 method with this structure as the initial structure. By performing molecular orbital calculation using the PM3 method for these most stable conformations, the “accessible volume” of each acid can be calculated. 1Å means 0.1 nm.
In this invention, the photo-acid generator which generate | occur | produces the acid illustrated below by irradiation of actinic light or a radiation is preferable. In addition, the calculated value of the volume is appended to a part of the example (unit ^{３ 3} ). In addition, the calculated value calculated | required here is a volume value of the acid which the proton couple | bonded with the anion part.

  Examples of the photoacid generator include paragraphs <0368> to <0377> of JP2014-41328A, paragraphs <0240> to <0262> of JP2013-228881A (corresponding US Patent Application Publication No. 2015/004533). <0339> of the specification can be incorporated, the contents of which are incorporated herein. Moreover, although the following compounds are mentioned as a preferable specific example, it is not limited to these.

A photo-acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the photoacid generator in the actinic ray-sensitive or radiation-sensitive resin composition is preferably 0.1 to 50% by mass, more preferably 5 to 50% by mass, based on the total solid content of the composition. More preferably, it is 8 to 40% by mass. In particular, in order to achieve both high sensitivity and high resolution at the time of electron beam or extreme ultraviolet exposure, the content of the photoacid generator is preferably high, more preferably 10 to 40% by mass, and most preferably 10 to 10% by mass. 35% by mass.

(C) Solvent When preparing the actinic ray-sensitive or radiation-sensitive resin composition by dissolving the above-described components, a solvent can be used. Examples of the solvent that can be used include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone having 4 to 10 carbon atoms, and ring having 4 to 10 carbon atoms. Examples thereof may include organic solvents such as monoketone compounds, alkylene carbonates, alkyl alkoxyacetates and alkyl pyruvates.

Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl Preferred examples include ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.
Preferred examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.

Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
Preferable examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.

  Examples of the cyclic lactone having 4 to 10 carbon atoms include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ- Caprolactone, γ-octanoic lactone, and α-hydroxy-γ-butyrolactone are preferred.

  Examples of the monoketone compound having 4 to 10 carbon atoms and optionally containing a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4- Methyl-2-pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2 -Hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4 -Heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-he Sen-2-one, 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopenta Non, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcyclo Preferred are heptanone and 3-methylcycloheptanone.

Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
Examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-acetate. 2-propyl is preferred.
Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.
As a solvent which can be preferably used, a solvent having a boiling point of 130 ° C. or higher under normal temperature and normal pressure can be mentioned. Specifically, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, acetic acid -2- (2-ethoxyethoxy) ethyl and propylene carbonate are mentioned.
In the present invention, the above solvents may be used alone or in combination of two or more.

In this invention, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group as an organic solvent.
Examples of the solvent containing a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate, and the like. Particularly preferred are propylene glycol monomethyl ether and ethyl lactate.
Examples of the solvent not containing a hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide and the like. Among these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, and butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate. 2-heptanone is most preferred.
The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, still more preferably 20/80 to 60 /. 40. A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.

  The solvent is preferably a mixed solvent of two or more containing propylene glycol monomethyl ether acetate. Of these, a combination of γ-butyllactone and butyl acetate is particularly preferred.

  As a solvent, the solvent of Paragraphs 0013-0029 of JP, 2014-219664, A can be used, for example.

(E) Basic compound The actinic ray-sensitive or radiation-sensitive resin composition preferably contains (E) a basic compound in order to reduce the change in performance over time from exposure to heating.
Preferred examples of the basic compound include compounds having structures represented by the following formulas (A1) to (E1).

In general formulas (A1) and (E1), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and are a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably carbon 3 to 20) or an aryl group (preferably having 6 to 20 carbon atoms), wherein R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring.

About the said alkyl group, as an alkyl group which has a substituent, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.
The alkyl groups in the general formulas (A1) and (E1) are more preferably unsubstituted.

  Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure Alternatively, a compound having a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, and the like can be given.

  Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, and benzimidazole. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5,4,0. ] Undec-7-ene etc. are mentioned. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris (t-butylphenyl) sulfonium. Examples thereof include hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. As the compound having an onium carboxylate structure, an anion portion of the compound having an onium hydroxide structure is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of the aniline compound include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

  Preferred examples of the basic compound further include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group.

As the amine compound, a primary, secondary or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. The amine compound is more preferably a tertiary amine compound. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the amine compound has an cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 3 to 20 carbon atoms). Preferably C6-C12) may be bonded to a nitrogen atom.
The amine compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is 1 or more, preferably 3 to 9, more preferably 4 to 6 in the molecule. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

As the ammonium salt compound, a primary, secondary, tertiary, or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the ammonium salt compound has a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group in addition to the alkyl group. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom.
The ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is 1 or more, preferably 3 to 9, more preferably 4 to 6 in the molecule. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or CH ₂ CH ₂ CH ₂ O—) is preferable, and oxyethylene is more preferable. It is a group.
Examples of the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable. As the halogen atom, chloride, bromide, and iodide are particularly preferable. As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy groups, acyl groups, and aryl groups. Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate. Examples of the aryl group of the aryl sulfonate include a benzene ring, a naphthalene ring, and an anthracene ring. The benzene ring, naphthalene ring and anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the linear or branched alkyl group and cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl, cyclohexyl and the like. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.

  The amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or ammonium salt compound. The phenoxy group may have a substituent. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. Etc. The substitution position of the substituent may be any of the 2-6 positions. The number of substituents may be any in the range of 1 to 5.

It is preferable to have at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups is 1 or more, preferably 3 to 9, more preferably 4 to 6 in the molecule. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

  The amine compound having a phenoxy group is prepared by reacting a primary or secondary amine having a phenoxy group with a haloalkyl ether by heating, and then adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. It can be obtained by extraction with an organic solvent such as ethyl acetate or chloroform. Alternatively, after reacting by heating a primary or secondary amine and a haloalkyl ether having a phenoxy group at the end, an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, tetraalkylammonium, etc. is added, and then ethyl acetate, It can be obtained by extraction with an organic solvent such as chloroform.

(A compound having a proton acceptor functional group and generating a compound that is decomposed by irradiation with actinic rays or radiation to decrease or disappear the proton acceptor property or change from a proton acceptor property to an acidic property (PA) )
The composition according to the present invention has a proton acceptor functional group as a basic compound, and is decomposed by irradiation with actinic rays or radiation, resulting in a decrease, disappearance, or a proton acceptor property. It may further contain a compound that generates a compound that has been changed to acidity (hereinafter also referred to as compound (PA)).

  The proton acceptor functional group is a group that can interact electrostatically with a proton or a functional group having an electron. For example, a functional group having a macrocyclic structure such as a cyclic polyether or a π-conjugated group. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure represented by the following general formula.

  Examples of a preferable partial structure of the proton acceptor functional group include a crown ether, an azacrown ether, a primary to tertiary amine, a pyridine, an imidazole, and a pyrazine structure.

  The compound (PA) is decomposed by irradiation with an actinic ray or radiation to generate a compound in which the proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity. Here, the decrease or disappearance of the proton acceptor property or the change from the proton acceptor property to the acid is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group. Specifically, when a proton adduct is formed from a compound having a proton acceptor functional group (PA) and a proton, the equilibrium constant in the chemical equilibrium is reduced.

  Specific examples of the compound (PA) include the following compounds. Furthermore, as specific examples of the compound (PA), for example, those described in paragraphs 0421 to 0428 of JP2014-41328A and paragraphs 0108 to 0116 of JP2014-134686A can be used. The contents of which are incorporated herein.

  These basic compounds are used alone or in combination of two or more.

  The usage-amount of a basic compound is 0.001-10 mass% normally on the basis of solid content of actinic-ray-sensitive or radiation-sensitive composition, Preferably it is 0.01-5 mass%.

  The use ratio of the photoacid generator and the basic compound in the composition is preferably photoacid generator / basic compound (molar ratio) = 2.5 to 300. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The photoacid generator / basic compound (molar ratio) is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

  As the basic compound, for example, compounds described in paragraphs 0140 to 0144 of JP2013-11833A (amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc.) can be used.

(A ′) Hydrophobic Resin The actinic ray-sensitive or radiation-sensitive resin composition may have a hydrophobic resin (A ′) separately from the resin (A).
The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film. However, unlike the surfactant, it is not always necessary to have a hydrophilic group in the molecule, and the polar / nonpolar substance is uniformly mixed. There is no need to contribute.
Examples of the effect of adding the hydrophobic resin include control of the static / dynamic contact angle of the resist film surface with respect to water, suppression of outgas, and the like.

The hydrophobic resin has at least one of “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer. It is preferable to have two or more types. The hydrophobic resin preferably contains a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on the side chain.

  When the hydrophobic resin contains a fluorine atom and / or a silicon atom, the fluorine atom and / or silicon atom in the hydrophobic resin may be contained in the main chain of the resin or in the side chain. It may be.

When the hydrophobic resin contains a fluorine atom, it may be a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom. preferable.
The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and further a fluorine atom It may have a substituent other than.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.
Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom. .
Examples of the repeating unit having a fluorine atom or a silicon atom include those exemplified in paragraph 0519 of US2012 / 0251948A1.

Further, as described above, the hydrophobic resin preferably includes a CH ₃ partial structure in the side chain portion.
Here, the CH ₃ partial structure contained in the side chain portion of the hydrophobic resin, is intended to encompass CH ₃ partial structure an ethyl group, and a propyl group having.
On the other hand, methyl groups directly bonded to the main chain of the hydrophobic resin (for example, α-methyl groups of repeating units having a methacrylic acid structure) contribute to the uneven distribution of the surface of the hydrophobic resin due to the influence of the main chain. Since it is small, it is not included in the CH ₃ partial structure in the present invention.

  Regarding the hydrophobic resin, the descriptions in <0348> to <0415> of JP-A No. 2014-010245 can be referred to, and the contents thereof are incorporated in the present specification.

  In addition, as the hydrophobic resin, those described in JP 2011-248019 A, JP 2010-175859 A, and JP 2012-032544 A can also be preferably used.

(F) Surfactant The actinic ray-sensitive or radiation-sensitive resin composition may further contain a surfactant (F). By containing a surfactant, when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less, is used, it is possible to form a pattern with less adhesion and development defects with good sensitivity and resolution. Become.
As the surfactant, it is particularly preferable to use a fluorine-based and / or silicon-based surfactant.
Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in <0276> of US Patent Application Publication No. 2008/0248425. F top EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafac F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troisol S-366 (manufactured by Troy Chemical Corporation); GF-300 or GF-150 (manufactured by Toa Gosei Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); EFtop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF 01 (manufactured by Gemco); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos) May be used. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition to known surfactants as described above, the surfactant is a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). You may synthesize. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991.
Further, surfactants other than fluorine-based and / or silicon-based surfactants described in <0280> of US Patent Application Publication No. 2008/0248425 may be used.

  One of these surfactants may be used alone, or two or more thereof may be used in combination.

  When the actinic ray-sensitive or radiation-sensitive resin composition contains a surfactant, the content thereof is preferably 0 to 2% by mass, more preferably 0.0001, based on the total solid content of the composition. ˜2 mass%, more preferably 0.0005 to 1 mass%.

(G) Other additives The actinic ray-sensitive or radiation-sensitive resin composition is a compound that promotes solubility in a dissolution inhibiting compound, dye, plasticizer, photosensitizer, light absorber, and / or developer. (For example, a phenol compound having a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxy group) may further be included.

The actinic ray-sensitive or radiation-sensitive resin composition may further contain a dissolution inhibiting compound.
Here, the “dissolution inhibiting compound” is a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce the solubility in an organic developer.

[Upper layer film (top coat film)]
In the pattern forming method of the present invention, an upper layer film (top coat film) may be formed on the resist film.
It is preferable that the upper layer film is not mixed with the resist film and can be uniformly applied to the upper layer of the resist film.
The upper layer film is not particularly limited, and a conventionally known upper layer film can be formed by a conventionally known method. For example, the upper layer film can be formed based on the description in paragraphs 0072 to 0082 of JP-A-2014-059543. As a material for forming the upper layer film, a hydrophobic resin or the like can be used in addition to the polymer described in paragraph 0072 of JP 2014-059543 A. As the hydrophobic resin, for example, the above-described hydrophobic resin (A ′) can be used.
In the development step, when using a developer containing an organic solvent, for example, an upper layer film containing a basic compound as described in JP2013-61648A is preferably formed on the resist film. . Specific examples of the basic compound that can be contained in the upper layer film include a basic compound (E).
The upper layer film preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond and an ester bond.
Furthermore, the upper layer film may contain a photoacid generator. As a photo-acid generator, the thing similar to the photo-acid generator (for example, photo acid generator (B) mentioned above) which can be contained in actinic-ray-sensitive or radiation-sensitive composition can be used.
Hereinafter, the resin that is preferably used for the upper layer film (top coat film) will be described.

(resin)
The composition for forming an upper layer film preferably contains a resin. The resin that can be contained in the composition for forming an upper layer film is not particularly limited, but is a hydrophobic resin that can be included in the actinic ray-sensitive or radiation-sensitive composition (for example, the above-described hydrophobic resin (A ′)) ) Can be used.
Regarding the hydrophobic resin, <0017> to <0023> of JP 2013-61647 A (corresponding <0017> to <0023> of US Published Patent Application 2013/244438) and JP 2014-56194 A. <0016> to <0165> can be referred to, and the contents thereof are incorporated in the present specification.
In the present invention, the composition for forming an upper layer film preferably contains a resin containing a repeating unit having an aromatic ring. By containing a repeating unit having an aromatic ring, the generation efficiency of secondary electrons and the efficiency of acid generation from a compound that generates an acid by actinic rays or radiation, particularly during electron beam or EUV exposure, are increased. High sensitivity and high resolution can be expected during formation.

  The weight average molecular weight of the resin is preferably 3000 to 100,000, more preferably 3000 to 30000, and most preferably 5000 to 20000. The amount of the resin in the composition for forming an upper layer film is preferably 50 to 99.9% by mass, more preferably 60 to 99.7% by mass, and still more preferably 70 to 99.5% by mass in the total solid content. 80 to 99.0 mass% is even more preferable.

When the composition for forming an upper layer film (topcoat composition) includes a plurality of resins, it is preferable to include at least one resin (XA) having a fluorine atom and / or a silicon atom.
The preferred range of the content of fluorine atoms and silicon atoms contained in the resin (XA) is preferably 10 to 100% by mass of the repeating unit containing fluorine atoms and / or silicon atoms in the resin (XA). It is preferable that it is -99 mol%, and it is more preferable that it is 20-80 mol%.

  Further, the composition for forming an upper layer film includes at least one resin (XA) having a fluorine atom and / or a silicon atom and a resin (XB) having a fluorine atom and / or silicon atom content smaller than the resin (XA). Is more preferable. Thereby, when the upper layer film is formed, the resin (XA) is unevenly distributed on the surface of the upper layer film, so that performance such as development characteristics and immersion liquid followability can be improved.

  The content of the resin (XA) is preferably 0.01 to 30% by mass, more preferably 0.1 to 10% by mass, based on the total solid content contained in the composition for forming an upper film, 8 mass% is still more preferable and 0.1-5 mass% is especially preferable. The content of the resin (XB) is preferably 50 to 99.9% by mass, more preferably 60 to 99.9% by mass, based on the total solid content contained in the composition for forming an upper layer film, and 70 to 99.99. 9 mass% is still more preferable, and 80-99.9 mass% is especially preferable.

  As the resin (XB), a form that substantially does not contain a fluorine atom and a silicon atom is preferable. In this case, specifically, the total content of the repeating unit having a fluorine atom and the repeating unit having a silicon atom is, 0-20 mol% is preferable with respect to all repeating units in resin (XB), 0-10 mol% is more preferable, 0-5 mol% is still more preferable, 0-3 mol% is especially preferable, and ideally Is 0 mol%, that is, does not contain fluorine atoms or silicon atoms.

<Method for Preparing Composition for Forming Upper Layer Film (Topcoat Composition)>
The composition for forming an upper layer film is preferably filtered by dissolving each component in a solvent. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon having a pore size of 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. Note that a plurality of types of filters may be connected in series or in parallel. Moreover, the composition may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step. Furthermore, you may perform a deaeration process etc. with respect to a composition before and after filter filtration. It is preferable that the composition for forming an upper layer film does not contain impurities such as metals. The content of the metal component contained in these materials is preferably 10 ppm or less, more preferably 5 ppm or less, still more preferably 1 ppm or less, and particularly preferably (not more than the detection limit of the measuring device). .

In the above <exposure step>, when the exposure is immersion exposure, the upper layer film is disposed between the actinic ray-sensitive or radiation-sensitive film and the immersion liquid, and the actinic ray-sensitive or radiation-sensitive film. It also functions as a layer that does not come into direct contact with the immersion liquid. In this case, preferable properties of the upper layer film (upper layer film forming composition) include suitability for application to an actinic ray-sensitive or radiation-sensitive film, transparency to radiation, particularly 193 nm, and immersion liquid (preferably Poorly soluble in water). Further, it is preferable that the upper layer film is not mixed with the actinic ray-sensitive or radiation-sensitive film and can be uniformly applied to the surface of the actinic-ray-sensitive or radiation-sensitive film.
In order to apply the composition for forming the upper layer film uniformly on the surface of the actinic ray sensitive or radiation sensitive film without dissolving the actinic ray sensitive or radiation sensitive film, the composition for forming the upper layer film is used. Preferably contains a solvent that does not dissolve the actinic ray-sensitive or radiation-sensitive film. As the solvent that does not dissolve the actinic ray-sensitive or radiation-sensitive film, it is more preferable to use a solvent having a component different from that of a developer containing an organic solvent (organic developer).

  The coating method of the composition for forming the upper layer film is not particularly limited, and a conventionally known spin coating method, spray method, roller coating method, dipping method, or the like can be used.

The thickness of the upper layer film is not particularly limited, but is usually 5 nm to 300 nm, preferably 10 nm to 300 nm, more preferably 20 nm to 200 nm, still more preferably 30 nm to 100 nm, from the viewpoint of transparency to the exposure light source. .
After forming the upper layer film, the substrate is heated (PB; PreBake) as necessary.
The refractive index of the upper layer film is preferably close to the refractive index of the actinic ray-sensitive or radiation-sensitive film from the viewpoint of resolution.
The upper layer film is preferably insoluble in the immersion liquid, and more preferably insoluble in water.
The receding contact angle of the upper layer film is preferably 50 to 100 degrees, more preferably 80 to 100 degrees, from the viewpoint of immersion liquid followability. More preferred.
In immersion exposure, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form an exposure pattern. The contact angle of the immersion liquid with respect to the light-sensitive or radiation-sensitive film is important, and in order to obtain better resist performance, it is preferable to have a receding contact angle in the above range.

  When peeling the upper layer film, an organic developer may be used, or a separate release agent may be used. As the release agent, a solvent having a small penetration into the actinic ray-sensitive or radiation-sensitive film is preferable. It is preferable that the upper layer film can be peeled off with an organic developer in that the upper layer film can be peeled off simultaneously with the development of the actinic ray-sensitive or radiation-sensitive film. The organic developer used for peeling is not particularly limited as long as it can dissolve and remove the low-exposed portion of the actinic ray-sensitive or radiation-sensitive film.

From the viewpoint of peeling with an organic developer, the upper layer film preferably has a dissolution rate in the organic developer of 1 to 300 nm / sec, more preferably 10 to 100 nm / sec.
Here, the dissolution rate of the upper layer film with respect to the organic developer is a rate of film thickness reduction when the upper layer film is formed and then exposed to the developer. In the present invention, the film was immersed in butyl acetate at 23 ° C. Speed.
By setting the dissolution rate of the upper layer film in the organic developer to 1 nm / sec or more, preferably 10 nm / sec or more, there is an effect of reducing development defects after developing the actinic ray-sensitive or radiation-sensitive film. is there. Further, by setting it to 300 nm / sec or less, preferably 100 nm / sec, the line edge of the pattern after developing the actinic ray-sensitive or radiation-sensitive film probably due to the effect of reducing the exposure unevenness during the immersion exposure. There is an effect that the roughness becomes better.
The upper layer film may be removed using another known developer, for example, an alkaline aqueous solution. Specific examples of the aqueous alkali solution that can be used include an aqueous solution of tetramethylammonium hydroxide.

[Content of organic impurities]
When a treatment liquid containing an organic solvent containing an organic impurity is applied to a semiconductor device manufacturing process, a high-boiling organic impurity having a boiling point of 300 ° C. or higher remains without volatilization, and the remarkably high degree. It tends to cause defects in the substrate.
In particular, the organic impurities having a boiling point of 300 ° C. or higher may be specifically a resin component or a plasticizer contained in a plastic material (for example, an O-ring) used for a member of a manufacturing apparatus, It is presumed that it was eluted in the liquid at any point in the manufacturing process.
When the content of the organic impurities having a boiling point of 300 ° C. or higher with respect to the total mass of the processing liquid is 0.001 mass ppm to 50 mass ppm, the development processing or the rinsing processing is performed when used in the semiconductor device manufacturing process. It was confirmed that it was within the range of defect defects that could reduce the number of defects by improving the conditions. In the treatment liquid, the content of the organic impurities having a boiling point of 300 ° C. or higher is more preferably 0.001 to 30 ppm by mass with respect to the total mass of the treatment liquid, and 0.001 to 15 ppm by mass. Is more preferable from the viewpoint of suppressing defect defects of the substrate when used in a semiconductor device manufacturing process, still more preferably 0.001 mass ppm to 10 mass ppm, and 0.001 mass ppm to 1 mass ppm. Most preferably.

When the content of organic impurities having a boiling point of 300 ° C. or higher is 30 mass ppm or less with respect to the total mass of the processing liquid, for example, when the processing liquid is used as a developer and brought into contact with the substrate, It is preferable from the viewpoint of suppressing organic impurities from remaining on the substrate surface without volatilizing and causing defective defects.
When the content of organic impurities having a boiling point of 300 ° C. or higher is 5 mass ppm or less with respect to the total mass of the processing solution, for example, when the processing solution is used as a developing solution and brought into contact with the substrate, baking is performed. In order to prevent organic impurities having a boiling point of 300 ° C. or higher from remaining on the substrate even after the process, it is more preferable from the viewpoint of suppressing the cause of defects (development failure).
In the treatment liquid, organic impurities at 300 ° C. or higher include components such as dioctyl phthalate (DOP, boiling point 385 ° C.) eluted from the O-ring, diisononyl phthalate (DINP, boiling point 403 ° C.), dioctyl adipate (DOA) , Boiling point 335 ° C.), dibutyl phthalate (DBP, boiling point 340 ° C.), ethylene propylene rubber (EPDM, boiling point 300 to 450 ° C.) and the like have been confirmed.

Content of the organic impurity whose boiling point in a process liquid is 300 degreeC or more is measured by DI-MS (direct injection mass chromatography).
Examples of the method for bringing the content of organic impurities having a boiling point in the treatment liquid of 300 ° C. or higher within the above range include the methods mentioned in the purification step described later.

<Metal component containing an element selected from the group consisting of Fe, Cr, Ni and Pb (metal impurity)>
In the present invention, the content of each metal component containing an element selected from the group consisting of Fe, Cr, Ni and Pb in the treatment liquid is 0.001 to 100 mass ppt with respect to the total mass of the treatment liquid. Preferably there is.
The metal component is present to a certain degree in the organic solvent, and may be mixed into the processing solution through these. Recently, it has been found that a metal component containing an element selected from the group consisting of Fe, Cr, Ni and Pb contained in the treatment liquid has a great influence on the defect performance.
If the content of the metal component containing an element selected from the group consisting of Fe, Cr, Ni, and Pb is 100 mass ppt or less with respect to the total mass of the treatment liquid, the defect suppressing ability is excellent and the mass is 1 mass ppt or less. In such a case, an excellent effect can be obtained by more remarkable defect suppressing ability.
In addition, when the content of the metal component containing an element selected from the group consisting of Fe, Cr, Ni and Pb exceeds 100 mass ppt with respect to the total mass of the processing liquid, it causes metal particles (deterioration of defects), If it exceeds 0.001 mass ppt, the production management can be performed stably, so the quality of each production lot is stabilized.
When a plurality of metal components containing an element selected from the group consisting of Fe, Cr, Ni and Pb are included, the total amount preferably satisfies the above range.
The content of metal impurities in the treatment liquid is measured by ICP-MS (inductively coupled plasma mass spectrometer). In addition, when the measurement was less than 1 mass ppt, it was difficult to measure with the stock solution. Therefore, the treatment liquid was concentrated as necessary for measurement.
Examples of the method for bringing the content of the metal impurities in the treatment liquid into the above range include the methods described in the purification step described later (for example, filter treatment using an ion exchange resin or a metal adsorbing member).

(substrate)
The “substrate” in the present invention includes, for example, a single-layer semiconductor substrate and a multi-layer semiconductor substrate.
The material constituting the semiconductor substrate composed of a single layer is not particularly limited, and is generally preferably composed of a group III-V compound such as silicon, silicon germanium, GaAs, or any combination thereof.
In the case of a multi-layer semiconductor substrate, the configuration is not particularly limited. For example, an exposed integration of interconnect features such as metal lines and dielectric materials on the above-described semiconductor substrate such as silicon. It may have a circuit structure. Metals and alloys used in the interconnect structure include, but are not limited to, aluminum and copper and alloyed aluminum, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten. Is not to be done. In addition, an interlayer dielectric layer, silicon oxide, silicon nitride, silicon carbide, carbon-doped silicon oxide, or the like may be provided on the semiconductor substrate.

<Processing liquid production method>
The treatment liquid of the present invention is preferably subjected to the following purification step in order to bring the contents of metal components, organic impurities having a boiling point of 300 ° C. or higher, and water into desired ranges.

(Purification process)
The purification step may be performed at any timing. Examples of the purification step include the following purification treatments I to IV.
That is, the purification treatment I is a treatment for purifying a raw material used for producing an organic solvent having a boiling point of less than 300 ° C. before producing the organic solvent having a boiling point of less than 300 ° C. constituting the treatment liquid.
Moreover, the refinement | purification process II is a process which refine | purifies this at the time of manufacture of the organic solvent whose boiling point is less than 300 degreeC which comprises a process liquid, and / or after manufacture.
Moreover, the refinement | purification process III is a process which refine | purifies for every component, before mixing the organic solvent whose boiling point is less than 300 degreeC at the time of manufacture of a process liquid.
Further, the purification treatment IV is a treatment for purifying the mixture after mixing two or more organic solvents having boiling points of less than 300 ° C. during the production of the treatment liquid.
As described above, purification is preferably performed to obtain a target treatment solution. The purification may be performed after individual organic solvents are purified, or may be purified after mixing the organic solvents. In particular, a method of blending purified organic solvents is preferable in that the blend ratio of the organic solvents can be made constant.
Each of the purification treatments I to IV may be performed only once, or may be performed twice or more.
The organic solvent to be used is purchased with high purity grade products (especially those having a low content of the above-mentioned organic impurities, metal impurities, water, etc.) and further subjected to a purification treatment to be described later. Can be used.

In the following, an example of the purification process is shown. In the following description, the objects to be purified in the purification process are simply referred to as “liquid to be purified”.
As an example of the purification process, a first ion exchange treatment for performing ion exchange treatment of a liquid to be purified, a dehydration treatment for dehydrating the liquid to be purified after the first ion exchange treatment, and distillation for performing distillation of the liquid to be purified after the dehydration treatment. A mode in which the second ion exchange treatment for performing the ion exchange treatment of the liquid to be purified after the treatment and the distillation treatment, and the organic impurity removal treatment for removing the organic impurities of the liquid to be purified after the second ion exchange treatment are performed in this order. Is mentioned. In the following, the above purification process will be described as an example, but the purification method for preparing the solution of the present invention is not limited to this. For example, first, a dehydration process for dehydrating the liquid to be purified is performed, a distillation process for distilling the liquid to be purified after the dehydration process, a first ion exchange process for performing an ion exchange process on the liquid to be purified, and a second ion The aspect which implements the organic impurity removal process which performs the organic impurity removal of the to-be-purified liquid after an exchange process in this order may be sufficient.

According to the first ion exchange treatment, ion components (for example, metal components) in the liquid to be purified can be removed.
In the first ion exchange treatment, first ion exchange means such as an ion exchange resin is used. The ion exchange resin includes a cation exchange resin or anion exchange resin provided in a single bed, a cation exchange resin and an anion exchange resin provided in multiple beds, and a mixed bed of a cation exchange resin and an anion exchange resin. Any of those provided in (1) may be used.
In addition, as the ion exchange resin, it is preferable to use a dry resin containing as little water as possible in order to reduce water elution from the ion exchange resin. As such a dry resin, a commercially available product can be used. 15JS-HG · DRY (trade name, dry cation exchange resin, moisture 2% or less) manufactured by Organo Corporation, and MSPS2-1 · DRY (trade name, Mixed bed resin, moisture 10% or less) and the like.

According to the dehydration treatment, water in the liquid to be purified can be removed. In addition, olefins can also be removed in the case of using a zeolite described later in the dehydration process (in particular, a molecular sieve (trade name) manufactured by Union Showa).
Examples of the dehydration means used in the dehydration treatment include a dehydration membrane, a water adsorbent that is insoluble in the liquid to be purified, an aeration apparatus using a dry inert gas, and a heating or vacuum heating apparatus.
When using a dehydration membrane, membrane dehydration by pervaporation (PV) or vapor permeation (VP) is performed. A dehydration membrane is constituted as a water-permeable membrane module, for example. As the dehydration membrane, a membrane made of a polymer material such as polyimide, cellulose, and polyvinyl alcohol, or an inorganic material such as zeolite can be used.
The water adsorbent is added to the liquid to be purified. Examples of the water adsorbent include zeolite, phosphorus pentoxide, silica gel, calcium chloride, sodium sulfate, magnesium sulfate, anhydrous zinc chloride, fuming sulfuric acid, and soda lime.

According to the distillation treatment, impurities eluted from the dehydration membrane, metal components in the liquid to be purified that are difficult to remove by the first ion exchange treatment, fine particles (including this if the metal component is fine particles), Water in the purified solution can be removed.
The distillation means is constituted by, for example, a single-stage distillation apparatus. Impurities are concentrated in the distillation apparatus or the like by distillation, but in order to prevent some of the concentrated impurities from flowing out, the distillation means regularly contains a part of the liquid in which the impurities are concentrated, Alternatively, it is preferable to provide means for constantly discharging to the outside.

According to the second ion exchange treatment, impurities accumulated in the distillation apparatus can be removed when they flow out, and eluate from a pipe such as stainless steel (SUS) used as a liquid feed line can be removed.
Examples of the second ion exchange means include an ion-exchange resin filled in a tower-like container and an ion adsorption film, and an ion adsorption film is preferable from the viewpoint that processing at a high flow rate is possible. An example of the ion adsorption film is Neoceptor (trade name, manufactured by Astom).

Each treatment described above is preferably performed in an airtight state and in an inert gas atmosphere where there is a low possibility that water will be mixed into the liquid to be purified.
Each treatment is preferably performed in an inert gas atmosphere having a dew point temperature of −70 ° C. or lower in order to suppress the mixing of moisture as much as possible. This is because, under an inert gas atmosphere of −70 ° C. or less, the moisture concentration in the gas phase is 2 mass ppm or less, so that the possibility of moisture entering the solution (liquid to be purified) is reduced.

  As the purification step, in addition to the above-described treatment, an adsorption purification treatment of a metal component using silicon carbide described in International Publication No. WO2012 / 043496 can be cited.

According to the organic impurity removal treatment, it is possible to remove high-boiling organic impurities and the like (including organic impurities having a boiling point of 300 ° C. or higher) that are contained in the liquid to be purified after the distillation treatment and are difficult to remove by the distillation treatment.
As an organic impurity removal means, it can implement by the organic impurity adsorption member provided with the organic impurity adsorption filter which can adsorb | suck an organic impurity, for example. In addition, the organic impurity adsorption member is usually configured to include the organic impurity adsorption filter and a base material on which the impurity adsorption filter is fixed.
From the viewpoint of improving the adsorption performance of organic impurities, the organic impurity adsorption filter has an organic substance skeleton capable of interacting with organic impurities on the surface (in other words, the surface is modified by an organic substance skeleton capable of interacting with organic impurities). Is preferable). Incidentally, having an organic substance skeleton capable of interacting with organic impurities on the surface means that the organic substance skeleton capable of interacting with the organic impurities is provided on the surface of the base material constituting the organic impurity adsorption filter described later. As an example.
Examples of the organic skeleton capable of interacting with the organic impurities include a chemical structure that can react with the organic impurities and trap the organic impurities in the organic impurity adsorption filter. More specifically, when organic impurities include dioctyl phthalate, diisononyl phthalate, dioctyl adipate, or dibutyl phthalate, the organic skeleton includes a benzene ring skeleton. Further, when ethylene propylene rubber is included as the organic impurity, examples of the organic skeleton include an alkylene skeleton. When n-long chain alkyl alcohol (structural isomer when 1-long chain alkyl alcohol is used as a solvent) is included as an organic impurity, the organic skeleton includes an alkyl group.
Examples of the base material (material) constituting the organic impurity adsorption filter include cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, fluororesin and the like supporting activated carbon.
Moreover, the filter which fixed the activated carbon of Unexamined-Japanese-Patent No. 2002-273123 and Unexamined-Japanese-Patent No. 2013-150979 to the nonwoven fabric can also be used for an organic impurity removal filter.

Further, the organic impurity removal treatment is not limited to an embodiment using an organic impurity adsorption filter capable of adsorbing organic impurities as described above, and may be an embodiment in which organic impurities are physically supplemented, for example. Organic impurities having a relatively high boiling point of 250 ° C. or higher are often coarse (for example, compounds having 8 or more carbon atoms) and can be physically supplemented by using a filter having a pore size of about 1 nm. It is.
For example, when dioctyl phthalate is included as an organic impurity, the structure of dioctyl phthalate is larger than 10 cm (= 1 nm). Therefore, by using an organic impurity removal filter having a pore diameter of 1 nm, dioctyl phthalate cannot pass through the pores of the filter. That is, since dioctyl phthalate is physically captured by the filter, it is removed from the liquid to be purified. Thus, the removal of organic impurities is possible not only by chemical interaction but also by applying a physical removal method. However, in this case, a filter having a pore diameter of 3 nm or more is used as a “filtration member” described later, and a filter having a pore diameter of less than 3 nm is used as an “organic impurity removal filter”.
In this specification, 1 Å (angstrom) corresponds to 0.1 nm.

Moreover, the purification process of the present invention may further include, for example, a purification process V and a purification process VI described later. The purification treatment V and the purification treatment VI may be performed at any timing, for example, after performing the purification step IV.
The purification process V is a filtering process using a metal ion adsorbing member for the purpose of removing metal ions.
Further, the purification treatment VI is a filtration treatment for removing coarse particles.
Hereinafter, the purification process V and the purification process VI will be described.

In the purification process VI, as an example of the metal ion removal means, filtering using a metal ion adsorption member provided with a metal ion adsorption filter can be cited as an example.
The metal ion adsorption member has a configuration including at least one metal ion adsorption filter, and may have a configuration in which a plurality of metal ion adsorption filters are stacked in accordance with a target purification level. The metal ion adsorption member is usually configured to include the metal ion adsorption filter and a base material on which the metal ion adsorption filter is fixed.
The metal ion adsorption filter has a function of adsorbing metal ions in the liquid to be purified. The metal ion adsorption filter is preferably an ion exchangeable filter.
Here, the metal ions to be adsorbed are not particularly limited, but are preferably Fe, Cr, Ni, and Pb from the viewpoint of easily causing defects in the semiconductor device.
The metal ion adsorption filter preferably has an acid group on the surface from the viewpoint of improving the adsorption performance of metal ions. Examples of the acid group include a sulfo group and a carboxy group.
Examples of the substrate (material) constituting the metal ion adsorption filter include cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, and fluororesin.

In the refinement | purification process VI, the aspect implemented using the filtration member provided with the filter whose particle removal diameter is 20 nm or less is mentioned as an example as a filtration means. The liquid to be purified can remove particulate impurities from the liquid to be purified by adding the filter. Here, the “particulate impurities” include particles such as dust, dust, organic solids and inorganic solids contained as impurities in the raw material used during the production of the liquid to be purified, and during purification of the liquid to be purified. Examples thereof include dust, dust, particles of organic solids and inorganic solids that are brought in as contaminants, and finally exist as particles without being dissolved in the liquid to be purified.
Further, “particulate impurities” include colloidal impurities containing metal atoms. Although it does not specifically limit as a metal atom, From Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, and Pb (preferably Fe, Cr, Ni, and Pb) When the content of at least one metal atom selected from the group consisting of these is particularly low (for example, when the content of the metal atom in the liquid to be purified is 1000 mass ppt or less, respectively), these metal atoms are contained. Impurities tend to colloid. In the metal ion adsorbing member, removal of colloidal impurities tends to be difficult. Therefore, by using a filter having a particle removal diameter of 20 nm or less (for example, a microfiltration membrane having a pore diameter of 20 nm or less), the colloidal impurities are effectively removed.
The particulate impurities have a size that can be removed by a filter having a particle removal diameter of 20 nm or less, specifically, particles having a diameter of 20 nm or more. In the present specification, particulate impurities may be referred to as “coarse particles”.
Especially, 1-15 nm is preferable and the particle removal diameter of the said filter has more preferable 1-12 nm. When the particle removal diameter is 15 nm or less, finer particulate impurities can be removed, and when the particle removal diameter is 1 nm or more, the filtration efficiency of the liquid to be purified is improved.
Here, the particle removal diameter means the minimum particle size that can be removed by the filter. For example, when the particle removal diameter of the filter is 20 nm, particles having a diameter of 20 nm or more can be removed.
Examples of the material of the filter include 6-nylon, 6, 6-nylon, polyethylene, polypropylene, polystyrene, and fluororesin.

  The filtration member may further include a filter having a particle removal diameter of 50 nm or more (for example, a microfiltration membrane for removing fine particles having a pore diameter of 50 nm or more). When fine particles are present in the solution in addition to colloidal impurities, particularly colloidal impurities containing metal atoms such as iron or aluminum, a filter having a particle removal diameter of 20 nm or less (for example, having a pore size of Prior to filtration using a 20 nm or less microfiltration membrane, the liquid to be purified is filtered using a filter having a particle removal diameter of 50 nm or more (for example, a microfiltration membrane for removing fine particles having a pore diameter of 50 nm or more). Thus, the filtration efficiency of a filter having a particle removal diameter of 20 nm or less (for example, a microfiltration membrane having a pore diameter of 20 nm or less) is improved, and the removal performance of coarse particles is further improved.

The to-be-purified liquid obtained by obtaining each of these treatments can be used for the composition of the treatment liquid of the present invention or as the treatment liquid itself of the present invention.
In addition, although the case where all each process was performed was shown as an example of the refinement | purification process mentioned above, it is not limited to this, Each said process may be performed independently and may carry out combining the said process in multiple numbers. . Moreover, each said process may be performed once and may be performed in multiple times.

  In addition to the above purification step, as a method for bringing the content of organic impurities, metal components and water having a boiling point of 300 ° C. or higher contained in the treatment liquid into a desired range, the boiling point constituting the treatment liquid is less than 300 ° C. The organic solvent raw material or the solution itself may be contained in a container with little impurity elution. In addition, a method of lining the inner wall of the pipe with a fluorine-based resin so that the metal component does not elute from the “pipe” or the like at the time of manufacturing the treatment liquid is also exemplified.

[Container (container)]
The treatment liquid of the present invention can be stored, transported and used by being filled in an arbitrary container as long as corrosivity and the like are not problematic.
As the container, a container having a high cleanliness in the container and little impurity elution is preferable for semiconductor applications.
Specific examples of containers that can be used include, but are not limited to, “Clean Bottle” series manufactured by Aicello Chemical Co., Ltd., “Pure Bottle” manufactured by Kodama Resin Co., Ltd., and the like. It is preferable that the inner wall of the container (the wetted part in contact with the solution in the container) is formed of a nonmetallic material.
Non-metallic materials include polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, tetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoride. Propylene copolymer resin (FEP), Tetrafluoroethylene-ethylene copolymer resin (ETFE), Trifluoroethylene chloride-ethylene copolymer resin (ECTFE), Vinylidene fluoride resin (PVDF), Trifluoroethylene chloride copolymer At least one selected from the group consisting of a resin (PCTFE) and a vinyl fluoride resin (PVF) is more preferable.
In particular, among the above, when using a container whose inner wall is made of a fluororesin, it is called elution of an ethylene or propylene oligomer as compared to using a container whose inner wall is a polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin. The occurrence of defects can be suppressed.
As a specific example of such a container whose inner wall is made of a fluororesin, for example, a FluoroPure PFA composite drum manufactured by Entegris may be mentioned. Also described on page 4 of Japanese Patent Publication No. Hei 3-502677, page 3 of International Publication No. 2004/016526 pamphlet, pages 9 and 16 of International Publication No. 99/46309 pamphlet, etc. These containers can also be used.
In addition, when setting it as the inner wall of a nonmetallic material, it is preferable that the elution to the process liquid of the organic component in a nonmetallic material is suppressed.

In addition to the above non-metallic materials, quartz or metal materials (more preferably, electropolished metal materials, in other words, electropolished metal materials) are preferably used for the inner wall of the container.
The metal material (in particular, a metal material used for producing an electropolished metal material) preferably contains chromium in an amount of more than 25% by mass with respect to the total mass of the metal material, for example, stainless steel.
The chromium content in the metal material is more preferably 30% by mass or more with respect to the total mass of the metal material. The upper limit is not particularly limited, but is generally preferably 90% by mass or less.

  The stainless steel is not particularly limited, and known stainless steel can be used. Especially, the alloy containing 8 mass% or more of nickel is preferable, and the austenitic stainless steel containing 8 mass% or more of nickel is more preferable. As austenitic stainless steel, for example, SUS (Steel Use Stainless) 304 (Ni content 8 mass%, Cr content 18 mass%), SUS304L (Ni content 9 mass%, Cr content 18 mass%), SUS316 ( Ni content 10 mass%, Cr content 16 mass%), SUS316L (Ni content 12 mass%, Cr content 16 mass%), etc. are mentioned.

  The method for electropolishing the metal material is not particularly limited, and a known method can be used. For example, methods described in paragraphs <0011>-<0014> of JP-A-2015-227501, paragraphs <0036>-<0042> of JP-A-2008-264929, and the like can be used.

It is presumed that the metal material is electropolished so that the chromium content in the passive layer on the surface is higher than the chromium content in the parent phase. Therefore, it is presumed that a metal component (metal impurity) -reduced solution can be obtained because the metal component hardly flows out from the inner wall covered with the electropolished metal material.
Note that the metal material is preferably buffed. The buffing method is not particularly limited, and a known method can be used. The size of the abrasive grains used for buffing finishing is not particularly limited, but is preferably # 400 or less in that the unevenness on the surface of the metal material tends to be smaller.
The buffing is preferably performed before the electrolytic polishing.
Further, the metal material may be processed by combining one or two or more of buff polishing, acid cleaning, magnetic fluid polishing, and the like performed at different stages such as the size of the abrasive grains. .

  In this invention, what has the said container and the said process liquid accommodated in this container may be called a solution container.

  It is preferable that the inside of these containers is washed before filling with the treatment liquid. When the treatment liquid of the present invention, a solution obtained by diluting the solution of the present invention, or an organic solvent contained in the treatment liquid of the present invention is used as the liquid for cleaning, the effects of the present invention are remarkably obtained. The processing liquid of the present invention may be transported and stored by bottling into a container such as a gallon bottle or a coated bottle after production. The gallon bottle may be one using a glass material or the other.

  In order to prevent changes in components in the processing liquid during storage, the inside of the container may be replaced with an inert gas (such as nitrogen or argon) having a purity of 99.99995 volume% or more. In particular, a gas having a low moisture content is preferable. Further, at the time of transportation and storage, the room temperature may be used, but the temperature may be controlled in a range of −20 ° C. to 20 ° C. in order to prevent deterioration.

(Clean room)
It is preferable that the treatment, analysis, and measurement including the production of the treatment liquid of the present invention, the opening and / or washing of the storage container, and the filling of the treatment liquid are performed in a clean room. The clean room preferably satisfies the 14644-1 clean room criteria. It is preferable to satisfy any of ISO (International Organization for Standardization) class 1, ISO class 2, ISO class 3, and ISO class 4, more preferably ISO class 1 or ISO class 2, and ISO class 1 More preferably. Production, treatment analysis, and measurement including treatment liquid production, unsealing and / or cleaning of the container, filling of treatment liquid, and the like in Examples described later were performed in a class 2 clean room.

(filtering)
The organic solvent contained in the treatment liquid of the present invention or the treatment liquid has a boiling point of the organic impurities, metal components, and water within a desired range, or removes foreign matters, coarse particles, etc. In order to do so, it is preferably filtered.
The filter used for filtering can be used without particular limitation as long as it has been conventionally used for filtration. Examples of the material constituting the filter include fluorine resins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, polyethylene resins, and polyolefin resins such as polypropylene (PP) (including high density and ultra high molecular weight). ) And the like. Among these, polyamide-based resin, PTFE, and polypropylene (including high-density polypropylene) are preferable, and by using a filter formed of these materials, it is more effective for highly polar foreign matters that easily cause particle defects. The amount of metal components (metal impurities) can be reduced more efficiently.

The critical surface tension of the filter is preferably 70 mN / m or more as the lower limit. As an upper limit, 95 mN / m or less is preferable. Especially, the critical surface tension of the filter is more preferably 75 mN / m or more and 85 mN / m or less.
In addition, the value of critical surface tension is a manufacturer's nominal value. By using a filter with a critical surface tension in the above range, it is possible to more effectively remove highly polar foreign substances that are likely to cause particle defects, and to reduce the amount of metal components (metal impurities) more efficiently. .

The filter used for filtering will not be specifically limited if it is conventionally used for the filtration use etc. Examples of the material constituting the filter include fluorine resins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, polyethylene resins, and polyolefin resins such as polypropylene (PP) (including high density and ultra high molecular weight). ) And the like. Among these, polypropylene (including high density polypropylene) and nylon are preferable.
The pore size of the filter is preferably about 0.001 to 1.0 μm, more preferably about 0.01 to 0.5 μm, and still more preferably about 0.01 to 0.1 μm. By setting the pore size of the filter in the above range, it is possible to reliably remove fine foreign substances contained in the treatment liquid or the organic solvent contained in the treatment liquid while suppressing filtration clogging.

When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, the filters may be of the same type or of different types, but of different types. It is preferable. Typically, the first filter and the second filter are preferably different in at least one of the hole diameter and the constituent material.
It is preferable that the second and subsequent pore diameters are the same or smaller than the first filtering pore diameter. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (former Nippon Microlith Co., Ltd.), KITZ Micro Filter Co., Ltd. In addition, “P-nylon filter (pore size 0.02 μm, critical surface tension 77 mN / m)” made of polyamide; (manufactured by Nippon Pole Co., Ltd.), “PE / clean filter (pore size 0.02 μm)” made of high-density polyethylene; (Manufactured by Nippon Pole Co., Ltd.) and “PE / clean filter (pore diameter 0.01 μm)” made by high-density polyethylene (made by Nippon Pole Co., Ltd.) can also be used.

Although not particularly limited, for example, in addition to a viewpoint that is superior due to the effect of the treatment liquid of the present invention, from the viewpoint of suppressing an increase in particulate metal in the storage of purified treatment liquid, the solution used in one embodiment of the present application, The relationship with the filter material used for filtering is included in the interaction radius (R0) in the Hansen solubility parameter (HSP) space, which can be derived from the filter material used for filtering, and the processing solution or the organic solvent contained in the processing solution. Is a combination satisfying the relational expression (Ra / R0) ≦ 1 of Ra and R0 when the radius of the sphere of the Hansen space that can be derived from the liquid to be derived (Ra) is filtered with a filter material that satisfies these relational expressions It is preferable that it is an organic solvent contained in a liquid or a process liquid. (Ra / R0) ≦ 0.98 is preferable, and (Ra / R0) ≦ 0.95 is more preferable. As a minimum, it is preferred that it is 0.5 or more, it is more preferred that it is 0.6 or more, and it is still more preferred that it is 0.7. The mechanism is not clear, but if it is within this range, the formation of particulate metal or the growth of particulate metal during long-term storage is suppressed.
A combination of these filters and a treatment liquid or an organic solvent contained in the treatment liquid is not particularly limited, and examples thereof include those disclosed in US Patent Publication No. 2016/0089622.

  As the second filter, a filter formed of the same material as the first filter described above can be used. The thing with the same hole diameter as the 1st filter mentioned above can be used. When a second filter having a pore diameter smaller than that of the first filter is used, the ratio of the second filter hole diameter to the first filter hole diameter (hole diameter of the second filter / hole diameter of the first filter). ) Is preferably 0.01 to 0.99, more preferably 0.1 to 0.9, and still more preferably 0.2 to 0.9. By setting the hole diameter of the second filter in the above range, fine foreign matters mixed in the solution are more reliably removed.

  Moreover, in this invention, it consists of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Pd, and Zn with respect to a process liquid or the organic solvent contained in a process liquid. When the content of one or more metal elements selected from the group is particularly low (for example, with respect to the treatment liquid or the organic solvent contained in the treatment liquid, the metal element content is 1000 masses each. In the case of less than ppt), impurities containing these metal elements tend to colloid. Therefore, removal of colloidal impurities tends to be difficult with an ion adsorption film. Thus, the present inventors have found that the colloidal impurity component can be removed by purification using a microfiltration membrane having a pore size of 20 nm or less.

  In addition, in the case where fine particles other than colloidal impurities (particularly colloidal impurities containing a metal element such as iron or aluminum) are present in the treatment liquid or the organic solvent solution contained in the treatment liquid It is preferable to purify by filtering using a microfiltration membrane for removing fine particles having a pore diameter of 50 nm or more before the filtration using a microfiltration membrane having a pore diameter of 20 nm or less.

  The treatment liquid of the present invention or the organic solvent contained in the treatment liquid is preferably purified using an ion adsorption means in addition to the filter as described above. In the ion adsorption means, the surface of cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, fluorine resin or the like is modified with an anionic group such as a sulfo group or a carboxy group, a cationic group, or both. It is preferable that it is an ion adsorption means. The ion adsorbing means modified with an anionic group can remove cations such as Na ions and Ca ions, and the ion adsorbing means modified with a cationic group can remove anions and acid components such as Cl ions. Can be removed. Depending on the purpose, the ion adsorbing means may use an anionic group, a cationic group or a combination of both. The ion adsorption means may be a filter.

  You may repeat said filtration process in multiple times according to the objective.

  Moreover, it is preferable to process the filter used before filtering the processing liquid or the organic solvent contained in the processing liquid. The liquid used for this treatment is not particularly limited, but the desired effect of the present invention is the solution itself of the present invention, a solution obtained by diluting the solution of the present invention, or an organic solvent contained in the treatment liquid of the present invention. Is remarkably obtained.

When filtering is performed, the upper limit of the temperature during filtering is preferably room temperature (25 ° C.) or less, more preferably 23 ° C. or less, and even more preferably 20 ° C. or less. Moreover, 0 degreeC or more is preferable, as for the lower limit of the temperature at the time of filtering, 5 degreeC or more is more preferable, and 10 degreeC or more is still more preferable.
Filtering can remove particulate foreign matters or impurities, but if performed at the above temperature, the amount of particulate foreign matters or impurities dissolved in the treatment liquid or the organic solvent contained in the treatment liquid is reduced. Filtering is performed more efficiently.

  In particular, from the viewpoint of adjusting the content of the metal component (metal impurity), it is preferable to filter at the above temperature. Although the mechanism is not clear, it is considered that many metal components (metal impurities) exist in a particulate colloidal state. When filtering at the above temperature, a part of the metal component (metal impurity) floating in the colloidal state aggregates, and this aggregated material is efficiently removed by filtering, so the metal component (metal It is conceivable that the content of (impurities) can be easily adjusted to a predetermined amount.

  Since the filtration pressure affects the filtration accuracy, the pressure pulsation during filtration is preferably as small as possible.

In the preparation and purification of the treatment liquid of the present invention or the organic solvent contained in the treatment liquid, the filtration rate is not particularly limited, but is preferably 0.6 L / min / m ² or more from the viewpoint of being superior due to the effects of the present invention. .75L / min / ^{m 2} or more preferably, 1.0 L / min / ^{m 2} or more is more preferable.
The filter is set with a differential pressure resistance that ensures filter performance (the filter is not broken). When this value is large, the filtration speed can be increased by increasing the filtration pressure. In other words, the upper limit of the filtration rate usually depends on the differential pressure resistance of the filter, but is usually preferably 10.0 L / min / m ² or less.

In the preparation and purification of the treatment liquid of the present invention or the organic solvent contained in the treatment liquid, the filtration pressure is preferably 0.001 MPa or more and 1.0 MPa or less, more preferably 0.003 MPa or more and 0.000 MPa or more, from the viewpoint of being excellent due to the effects of the present invention. 5 MPa or less is more preferable, and 0.005 MPa or more and 0.3 MPa or less is particularly preferable.
In particular, when a filter having a small pore size is used, the amount of particulate foreign matters or impurities dissolved in the solution can be efficiently reduced by increasing the filtration pressure. When using a filter having a pore size smaller than 20 nm, it is particularly preferable that the filtration pressure is 0.005 MPa or more and 0.3 MPa or less.

  In addition, when the pore size of the filtration filter membrane decreases, the filtration speed decreases.For example, by connecting a plurality of filters equipped with the same type of filtration filter membrane in parallel, the filtration area is expanded and the filtration pressure is increased. This makes it possible to compensate for the reduction in filtration rate.

[Static elimination process]
The preparation and purification of the treatment liquid of the present invention or the organic solvent contained in the treatment liquid may further have a static elimination step. The static elimination step is a step of reducing the charged potential of the purified product, etc., by neutralizing at least one selected from the group consisting of raw materials, reactants, and purified product (hereinafter referred to as “purified product etc.”). .
The static elimination method is not particularly limited, and a known static elimination method can be used. Examples of the static elimination method include a method of bringing the purified liquid or the like into contact with a conductive material.
The contact time for contacting the purified liquid or the like with the conductive material is preferably 0.001 to 60 seconds, more preferably 0.001 to 1 second, and still more preferably 0.01 to 0.1 second. Examples of the conductive material include stainless steel, gold, platinum, diamond, and glassy carbon.
Examples of the method for bringing the purified liquid or the like into contact with the conductive material include a method in which a grounded mesh made of a conductive material is disposed inside the pipe and the purified liquid or the like is passed therethrough.

  The static elimination step may be performed at any point from the raw material supply to the filling of the purified product, for example, selected from the group consisting of the raw material supply step, reaction step, liquid preparation step, purification step, filtration step, and filling step It is preferably contained before at least one step. In particular, it is preferable to perform the static elimination step before injecting the purified product or the like into the container used in each of the above steps. Thereby, it can suppress that the impurity originating in a container etc. mixes in a refined material.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.
In addition, the quantitative analysis (for example, JISK2541-6: 2013 “sulfur content test” of the sulfur-containing compound with respect to the processing solution used in the subsequent development or rinsing (the processing solution described in Table 8 and Table 8-Part 2). Measured by the method defined in “Method (Ultraviolet Fluorescence Method)” and quantitative analysis of phosphorus compounds (measured by spectrophotometry as total phosphorus based on the method defined in JISK0102: 2013) It was confirmed that the compound was not substantially contained.
Here, “substantially does not contain” means that it is not detected (below the detection limit value) when the content (concentration) of these compounds is measured by a measurable method.

1. EUV exposure (Examples 1-1 to 1-44, Comparative Examples 1-1 to 1-2)
<Resin (A), etc.>
(Synthesis Example 1) Synthesis of Resin (A-1) 600 g of cyclohexanone was placed in a 2 L flask and purged with nitrogen at a flow rate of 100 mL / min for 1 hour. Thereafter, 4.60 g (0.02 mol) of a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the temperature was raised until the internal temperature reached 80 ° C. Next, the following monomers and 4.60 g (0.02 mol) of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 200 g of cyclohexanone to prepare a monomer solution. The monomer solution was dropped into the flask heated to 80 ° C. over 6 hours. After completion of dropping, the reaction was further continued at 80 ° C. for 2 hours.
4-acetoxystyrene ... 48.66 g (0.3 mol)
1-ethylcyclopentyl methacrylate ... 109.4 g (0.6 mol)
Monomer 1 ... 22.2 g (0.1 mol)

  The reaction solution was cooled to room temperature and dropped into 3 L of hexane to precipitate a polymer. The filtered solid was dissolved in 500 mL of acetone, dropped again into 3 L of hexane, and the filtered solid was dried under reduced pressure to obtain 160 g of 4-acetoxystyrene / 1-ethylcyclopentyl methacrylate / monomer 1 copolymer (A-1). It was.

  10 g of the polymer obtained above, 40 mL of methanol, 200 mL of 1-methoxy-2-propanol and 1.5 mL of concentrated hydrochloric acid were added to the reaction vessel, heated to 80 ° C. and stirred for 5 hours. The reaction solution was allowed to cool to room temperature and dropped into 3 L of distilled water. The filtered solid was dissolved in 200 mL of acetone, dropped again into 3 L of distilled water, and the filtered solid was dried under reduced pressure to obtain Resin (A-1) (8.5 g). The weight average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography (GPC) (solvent: THF (tetrahydrofuran)) was 11,200, and the molecular weight dispersity (Mw / Mn) was 1.45.

Resins (A-2) to (A-19) and (A-21) to (A-23) having the structures shown in Table 1 were prepared in the same manner as in Synthesis Example 1 except that the monomers used were changed. Synthesized.
In Table 1, the composition ratio (molar ratio) of the resin was calculated by ¹ H-NMR (nuclear magnetic resonance) measurement. The weight average molecular weight (Mw: polystyrene conversion) and dispersity (Mw / Mn) of the resin were calculated by GPC (solvent: THF) measurement. In addition, the weight average molecular weight and dispersity were measured by the same method also about other resin shown in an Example.

<Hydrophobic resin (A ')>
The following were used as the hydrophobic resin.

  Hereinafter, specific structural formulas of the resins (1b) to (5b) described in the table are shown below.

<Photoacid generator (B)>
As the photoacid generator, the following were used.

<Basic compound (E)>
The following were used as basic compounds.

<Solvent (C)>
The following resist solvents were used.
C-1: Propylene glycol monomethyl ether acetate C-2: Propylene glycol monomethyl ether C-3: Ethyl lactate C-4: Cyclohexanone C-5: Anisole

<Resist composition>
Each component shown in the following Table 5 was dissolved in the solvent shown in the same table. This was filtered using a polyethylene filter having a pore size of 0.03 μm to obtain a resist composition.

<Composition for forming upper layer film>
Each component shown in the following Table 6 was dissolved in the solvent shown in the same table. This was filtered using a polyethylene filter having a pore size of 0.03 μm to obtain a composition for forming an upper layer film. In the table below, “MIBC” represents methyl isobutyl carbinol.

The resins V-1 to V-4, 1b and additive X1 used below are shown. Other additives are the same as those described above.
The composition ratio, weight average molecular weight, and degree of dispersion of the resins V-1 to V-4, 1b are shown in Table 7 below.

<EUV exposure evaluation>
Using the resist compositions described in Table 5, the post-development defect performance and pattern formation performance of the resist were evaluated by the following operations.
[Application of resist composition and baking after application (PB)]
Each resist composition obtained as described above was applied onto a 12-inch silicon wafer and baked at 90 to 180 ° C. for 60 seconds to form a resist film having a thickness of 40 nm.
In addition, Example 1-24 is a positive resist composition, and other than that is a negative resist composition.

[Coating of composition for forming upper layer film and baking after coating (PB)]
For the examples in Table 9 and Table 9-Part 2 described later, the upper layer film-forming composition (top coat composition) shown in Table 9 and Table 9-Part 2 was applied onto the resist film after baking. Thereafter, baking was performed for 60 seconds at the PB temperatures (unit: ° C.) shown in Table 9 and Table 9-Part 2 to form an upper film (top coat) having a thickness of 40 nm.

〔exposure〕
(Defect performance evaluation after development)
The wafer prepared above was subjected to EUV exposure with NA (Numerical Aperture) 0.25 and dipole illumination (Dipole 60x, outer sigma 0.81, inner sigma 0.43). Specifically, a negative resist is exposed at a dose of 1 mJ / cm ² without a mask, and a positive resist is masked at a dose of 200 mJ / cm ^2. The entire surface was exposed without intervention.

(CH missing performance (CH pattern missing, C / H missing) evaluation)
The wafer produced as described above was subjected to EUV exposure with NA (lens numerical aperture) 0.25 and Quasar illumination (Quasar 45, outer sigma 0.81, inner sigma 0.51). Specifically, EUV with different exposure dose through a mask containing a pattern for forming a contact hole pattern having a pitch on the wafer of 60 nm and a hole size of 30 nm (for evaluating C / H detachability). Exposure was performed.

[Post-exposure bake (PEB)]
After the irradiation, the sample was taken out from the EUV exposure apparatus, and immediately baked for 60 seconds at 85 to 130 ° C.

〔developing〕
Then, using a shower type developing device (ADE3000S manufactured by ACTES Co., Ltd.), spray the developer (23 ° C.) at a flow rate of 200 mL / min for 30 seconds while rotating the wafer at 50 rotations (rpm). Then, development was performed. In addition, as a developing solution, the processing liquid in any one of S-1 to S-50 was used. The processing solutions used in each example and comparative example are shown in Table 8 and Table 8-Part 2. In addition, the mixing ratio in Table 8 and Table 8-Part 2 represents the organic solvent described in Table 8 and Table 8-Part 2 in order from the left side.

(In-plane CD variation after etching)
A wafer was formed by patterning a resist film made of each resist composition on a 12-inch silicon wafer having an oxide film with a thickness of 100 nm formed on the surface layer. In addition, the pattern was such that a pattern having a shot size of 20 mm × 30 mm on the wafer was subjected to EUV exposure by the exposure method described in the above-mentioned post-development defect performance evaluation.
An oxide film pattern was obtained on the wafer by performing sequential processing under the conditions of the following etching conditions 1 and 2 using the created pattern as an etching mask.
For the oxidized pattern after the etching treatment, 80 shots on the wafer were observed with a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.) at a magnification of 200 k, and the hole size and line line were observed within the observed field of view. The width was determined. The in-plane distribution of the line width or hole size obtained at each shot position was determined, and the in-plane CD variation after etching was determined with the sigma value as the in-plane CD variation.
(Etching conditions)
Equipment: AMAT Centura / e-Max Oxide Etcher
(Etching condition 1)
Source / Bias: 250W / 25W
Pressure: 7.5mTorr
Substrate temperature: 35 ° C
CHF3 / SF6 / Ar = 40/5/55 sccm
Time: 60 seconds (etching condition 2)
Source / Bias: 250W / 25W
Pressure: 7.5mTorr
Substrate temperature: 35 ° C
O2 / Ar = 20/55 sccm
Time: 60 seconds

Each treatment solution was purified as follows.
For purification of the treatment liquid or the organic solvent contained in the treatment liquid, an apparatus in which a “dehydration member” is connected to the downstream side of the second metal ion adsorption filter 34 of the organic solvent purification apparatus 100 of FIG.
Here, in the organic solvent refining apparatus 100 of FIG. 1 used in the example column, the tank 10 used was a stainless steel liquid contact part coated with PTFE. Moreover, the pump 20 used what the liquid-contact part was coated with PTFE. In addition, a PFA tube having an outer diameter of 12 mm was used for the supply pipe 60.
The distillation unit 50 was a shelf-type distillation tower (10 stages (10 shelves)) made of SUS316.
As the first metal ion adsorption filter 32 and the second metal ion adsorption filter 34, 15 nm IEX PTFE (filter having a pore size of 15 nm having a sulfo group on the surface of a PTFE base material) manufactured by Entegris was used.
Further, 12 nm PTFE manufactured by Entegris (a filter having a particle removal diameter of 12 nm manufactured by PTFE) was used as the filtration member 40. Moreover, the filter which fixed the activated carbon of Unexamined-Japanese-Patent No. 2013-150979 to the nonwoven fabric was used for the organic impurity adsorption member 50. FIG.
And after filling each organic solvent of Table 1 into the tank 10, according to the direction of the arrow of FIG. 1, the to-be-purified substance was circulated once, and the organic solvent contained in the processing liquid or the processing liquid was obtained. .

<Evaluation>
[Measurement of metal components (metal impurities)]
The content of metal atoms contained in the metal impurities in the processing solutions prepared in each Example and Comparative Example was measured using an Agilent 8800 triple quadrupole ICP-MS (for semiconductor analysis, option # 200).
(Measurement condition)
In order to measure the content of metal atoms contained in the metal impurities in the treatment liquid prepared in each of the examples and comparative examples, a quartz torch, a coaxial PFA (perfluoroalkoxyalkane) nebulizer (for self-priming), and A platinum interface cone was used. The measurement parameters for the cool plasma conditions are as follows.
-RF (Radio Frequency) output (W): 600
Carrier gas flow rate (L / min): 0.7
-Makeup gas flow rate (L / min): 1
-Sampling depth (mm): 18
[Measurement of organic impurities with boiling point of 300 ° C or higher]
The content of organic impurities having a boiling point of 300 ° C. or higher in the treatment liquid was measured by DI-MS (direct injection mass chromatography).

〔rinse〕
Then, the rinse process was performed by spraying a rinse liquid (23 degreeC) for 15 second by the flow volume of 200 mL / min, rotating a wafer by 50 rotations (rpm).
Finally, the wafer was dried by high-speed rotation at 2500 rotations (rpm) for 60 seconds. In addition, as a rinse liquid, the process liquid in any one of S-1 to S-50 was used. Table 9 and Table 9-Part 2 (compositions are Table 8 and Table 8-Part 2) show the rinsing solutions used in Examples and Comparative Examples. When there is no description of the rinse solution in Table 9 and Table 9-Part 2 (composition is Table 8 and Table 8-Part 2), it indicates that the rinse treatment is not performed after development.

〔Evaluation test〕
For the following items, performance evaluation was performed on wafers that had been exposed and developed. Details of the results are shown in Table 9 and Table 9-2.

(Defect performance evaluation after development)
The number of particles having a diameter of 19 nm or more (hereinafter referred to as “defects”) present on the surface of the post-development defect evaluation wafer created as described above was measured by a wafer surface inspection apparatus (SP-5; manufactured by KLA Tencor). Thereafter, each defect was subjected to elemental analysis by EDAX. Of these, those containing a metal component were defined as metal particles, and defects containing only the organic component but not the metal component were defined as organic residues. Evaluation of defects after development of metal particles and evaluation of defects after development of organic residues were evaluated according to the following criteria. The smaller the number of defects, the better the performance. In the following criteria, if the evaluation is “D” or higher, the defect level required in the semiconductor device manufacturing process is achieved.
“A”: The number of defects is 200 or less “B”: The number of defects is more than 200 and less than 500 “C”: The number of defects is more than 500 and less than 1000 “D”: The number of defects is more than 1000 and less than 1500 “E”: The number of defects Over 1500

(CH missing performance (CH pattern missing, C / H missing) evaluation)
The resolution of contact hole patterns exposed at different exposure doses was observed with a scanning electron microscope (S-9380II, manufactured by Hitachi, Ltd.) at a magnification of 200 k. The minimum hole size at which no defect occurred was obtained and used as an index of CH removal performance. The smaller this value, the better the CH removal performance.

2. ArF immersion exposure (Examples 2-1 to 2-45, Comparative Examples 2-1 to 2-2)
Using the resist composition described in Table 5 above, a resist pattern was formed by the following operation.

[Application of resist composition and baking after application (PB)]
Each resist composition obtained as described above was applied onto a 12-inch silicon wafer and baked at 90 to 120 ° C. for 60 seconds to form a resist film having a thickness of 40 nm.
When performing the CH pattern evaluation, before applying the resist film, an organic antireflection film ARC29SR (made by Brewer) is applied on the silicon wafer and baked at 205 ° C. for 60 seconds to make a reflection with a thickness of 86 nm. A prevention film was formed.

[Coating of composition for forming upper layer film and baking after coating (PB)]
The composition for forming an upper layer film (top coat composition) shown in Table 6 above is applied on the resist film after baking, and then at the PB temperatures (unit: ° C.) shown in Table 10 and Table 10-2. Baking was performed for 60 seconds to form an upper film (top coat) having a thickness of 40 nm.

〔exposure〕
(Defect performance evaluation after development)
Using the ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.750, inner sigma 0.650, Y deflection) on the wafer prepared above, 1 mJ / cm ² The entire surface exposure was performed without using a mask at the exposure amount of. Ultra pure water was used as the immersion liquid. Then, it heated for 60 second on conditions (90-120 degreeC) (PEB: Post Exposure Bake). Next, using a developing device (manufactured by SOKUDO; RF ³ ), the developers described in Table 10 and Table 10-Part 2 below (for each developer, see Table 8 and Table 8-Part 2) are 30. Table 10 and Table 10-Part 2 below while rotating the wafer at 50 rpm (rpm) (see Table 8 and Table 8-Part 2 for each rinse) ) For 15 seconds. Subsequently, by rotating the wafer for 30 seconds at a rotational speed of 2000 rpm, a defect evaluation wafer was prepared in which the resist film was developed and removed over the entire surface of the wafer.

(CH missing performance (CH pattern missing, C / H missing) evaluation)
Using the ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.730, inner sigma 0.630, XY deflection) on the wafer produced above, the hole portion is 65 nm. Then, the resist film was subjected to pattern exposure by changing the exposure amount through a square array 6% halftone mask (hole portions were shielded) with a pitch between holes of 100 nm. Ultra pure water was used as the immersion liquid. Then, it heated for 60 second on conditions (90-120 degreeC) (PEB: Post Exposure Bake). Next, using a developing device (manufactured by SOKUDO; RF ³ ), the developers described in Table 10 and Table 10-Part 2 below (for each developer, see Table 8 and Table 8-Part 2) are 30. Table 10 and Table 10-Part 2 below while rotating the wafer at 50 rpm (rpm) (see Table 8 and Table 8-Part 2 for each rinse) The hole pattern was obtained by rinsing for 15 seconds, and then rotating the wafer for 30 seconds at a rotational speed of 2000 rpm. In addition, when there is no description of a rinse solution in a table | surface, it represents that the rinse process is not performed after image development.
(In-plane CD variation after etching)
In-plane CD variation after etching was evaluated in the same manner except that the evaluation method for post-etching in-plane CD variation in the EUV exposure and the exposure method were ArF immersion exposure in the post-development defect performance evaluation described above.

〔Evaluation test〕
For the same items as the “EUV exposure evaluation” described above, the resist pattern was evaluated by the same method using “S-9380II” (manufactured by Hitachi, Ltd.) as a scanning electron microscope. Details of the results are shown in Table 10 and Table 10-Part 2.

3. Evaluation results As shown in the above examples of Table 9, Table 9-Part 2, Table 10, and Table 10-Part 2, in any case where any exposure light source is used, an organic solvent having a boiling point of 172 ° C. or higher is 30% or more. It was found that when the contained treatment liquid was used, the metal particle defect performance and the CH pattern removal were good.
This is presumably because an organic solvent having a boiling point of 172 ° C. or higher is likely to remain in the resist film, thereby increasing the effect of washing away insoluble components in the resist film.
Further, it was found that all the examples had good effects of post-development defect evaluation and in-plane CD variation after etching.

  In addition, it can be confirmed that the treatment liquid of the present invention can be applied to both a negative resin and a positive resin.

  The treatment liquid of the present invention is applied to a FluoroPure PFA composite drum manufactured by Entegris (wetted inner surface; PFA resin lining) and a steel drum can made from JFE (wetted inner surface; zinc phosphate coating) as described in JP-A-2014-112176. Then, after 14 days storage at room temperature, wet particles (indicating defects due to organic residue among the defects detected in development defect evaluation), organic impurity concentration analysis, and metal particle impurity concentration analysis are performed. FluoroPure PFA composite drum (wetted inner surface; PFA resin lining) manufactured by Entegris was able to obtain better results than a drum can (wetted inner surface; zinc phosphate coating).

DESCRIPTION OF SYMBOLS 10 Tank 20 Pump 32 1st metal ion adsorption filter 34 2nd metal ion adsorption filter 40 Filtration member 50 Distilling part 50 Organic impurity adsorption member 60 Supply pipe 100 Organic solvent refinement | purification apparatus

Claims (20)

(A) forming a resist film using an actinic ray-sensitive or radiation-sensitive composition;
(B) exposing the film;
(C) a pattern forming method including a step of processing the exposed film using a processing liquid,
The said process liquid is a pattern formation method which contains 30 mass% or more of organic solvents whose standard boiling point is 172 degreeC or more.   The pattern forming method according to claim 1, wherein a normal boiling point of the organic solvent is 175 ° C. or higher.   The pattern forming method according to claim 1, wherein the step (c) includes a step of developing the exposed film using the processing liquid.   The step (c) includes a step of developing the exposed film and a step of rinsing the developed film, and the processing liquid is used in at least one of the developing step and the rinsing step. The pattern forming method according to claim 1 or 2, wherein:   The pattern formation method according to claim 1, wherein the treatment liquid further includes an ester solvent.   The ester solvent is selected from butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, butyl isobutanoate, and butyl butanoate. The pattern forming method according to claim 5, comprising at least one selected from the group consisting of:   The pattern formation method according to claim 1, wherein the treatment liquid further includes a ketone solvent.   The pattern formation method according to claim 7, wherein the ketone solvent contains at least one selected from methyl isoamyl ketone, cyclohexane, cyclopentanone, methyl ethyl ketone, and 2-heptanone.   The said composition contains the resin provided with the group which decomposes | disassembles by the effect | action of an acid, and produces | generates a polar group, and the compound which generate | occur | produces an acid by irradiation of actinic light or a radiation. Pattern forming method.   The pattern forming method according to claim 1, wherein the step (b) is performed using a KrF or ArF excimer laser.   The pattern forming method according to claim 1, wherein the step (b) is performed using EUV light.   (D) The pattern formation method of any one of Claim 1 to 11 which further included the process of heating the film | membrane processed using the said process liquid.   The pattern formation method according to any one of claims 1 to 12, wherein the treatment liquid contains 0.001 to 30 mass ppm of an organic impurity having a boiling point of 300 ° C or higher with respect to the total mass of the treatment liquid.   The pattern formation method of any one of Claim 1 to 13 whose moisture content of the said process liquid is 500 ppm or less. A processing liquid used in the pattern forming method according to claim 1,
A treatment liquid containing 30% by mass or more of an organic solvent having a standard boiling point of 172 ° C. or higher.   The processing liquid according to claim 15, which is used for developing the exposed film.   The processing solution according to claim 15, which is used for rinsing the developed film.   The treatment liquid according to any one of claims 15 to 17, wherein the treatment liquid contains 0.001 to 30 mass ppm of an organic impurity having a boiling point of 300 ° C or higher with respect to the total mass of the treatment liquid.   The processing solution contains an element selected from the group consisting of Fe, Cr, Ni and Pb, and the content of each element is 0.001 to 100 mass ppt with respect to the total mass of the processing solution. The processing liquid according to any one of 18.   The processing liquid according to any one of claims 15 to 19, which is generated through a distillation and filtration process.