JP6858689B2 - Treatment liquid and pattern formation method - Google Patents

Description

The present invention relates to a treatment liquid and a pattern forming method.
More specifically, the present invention is used in semiconductor manufacturing processes such as ICs (Integrated Circuits), manufacturing of circuit boards such as liquid crystal and thermal heads, and other photolithography lithography processes. The present invention relates to a treatment liquid and a pattern forming method.

Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integrated Circuits), fine processing by lithography using a photoresist composition has been performed. In recent years, with the increasing integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quartermicron region has been required. Along with this, there is a tendency for the exposure wavelength to be shortened from g-line to i-line and further to KrF excimer laser light. Furthermore, at present, in addition to excimer laser light, lithography using electron beam, X-ray, or EUV light (Extreme Ultra Violet) is also under development.
In such lithography, a film is formed with a photoresist composition (also referred to as a photosensitive light or radiation-sensitive composition or a chemically amplified resist composition), and then the obtained film is developed with a developing solution. , The developed film is washed with a rinsing solution.
For example, Patent Document 1 discloses that a treatment 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.

Japanese Unexamined Patent Publication No. 2012-181523

In recent years, with the increasing integration of integrated circuits, the formation of fine patterns using a photoresist composition (sensitive light ray or radiation sensitive composition) has been required. In the formation of such a fine pattern, a developing solution and a rinsing solution that do not generate defects are required because even a slight defect affects the operation of the semiconductor chip. On the other hand, in recent years, the required characteristics of the pattern formed from the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition have become higher, and in particular, further reduction of LWR (Line Width Roughness) has been required. ..

However, the current situation is that no developer or rinse solution that can simultaneously achieve low defect performance and improved LWR performance in a fine pattern is known.

The present invention has been made in view of the above points, and an object of the present invention is to provide a treatment liquid and a pattern forming method for resist film patterning, which can simultaneously suppress the generation of defects on the resist and improve the resist LWR performance. And.

As a result of diligent studies on the above problems, the present inventors have found that a desired effect can be obtained by using a treatment liquid containing at least two kinds of organic solvents having an SP value in a specific range in combination.
That is, the present invention provides the following [1] to [21].
[1] (a) a step of forming a resist film using a sensitive light beam or a radiation-sensitive composition, (b) a step of exposing the film, and (c) the exposed film using a treatment liquid. ^{The treatment liquid contains 2 or more organic solvents having an SP value of 16.3 MPa 1/2} or more, and at least one of the above 2 or more organic solvents is included in the pattern forming method. Is a pattern forming method in which the SP value is 17 to 18.2 MPa ^1/2.
[2] The pattern forming method according to [1], wherein the step (c) includes a step of developing the exposed film using the treatment liquid.
[3] The step (c) includes a step of developing the exposed film and a step of rinsing the developed film, and in at least one of the developing step and the rinsing step, the above-mentioned treatment The pattern forming method according to [1], wherein a liquid is used.
[4] The pattern forming method according to any one of [1] to [3], which comprises an ester solvent as an organic solvent having an SP value of 17 to 18.2.
[5] The above ester solvents are butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, isobutyl isobutate, and butanoic acid. The pattern forming method according to [4], which is a solvent containing at least one selected from butyl.
[6] The pattern forming method according to any one of [1] to [3], which comprises a ketone solvent as an organic solvent having an SP value of 17 to 18.2.
[7] The pattern forming method according to [6], wherein the ketone solvent is a solvent containing at least one selected from methyl isoamyl ketone, methyl isobutyl ketone, diisobutyl ketone and 2-heptanone.
[8] Any of [1] to [7], wherein the composition contains 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 by irradiation with active light or radiation. The pattern forming method described in Crab.
[9] The pattern forming method according to any one of [1] to [8], wherein the step (b) is performed using a KrF or ArF excimer laser.
[10] The pattern forming method according to any one of [1] to [8], wherein the step (b) is performed using EUV light.
[11] (d) The pattern forming method according to any one of [1] to [10], further comprising heating the film treated with the above-mentioned treatment liquid.
[12] The pattern forming method according to any one of [1] to [11], which contains 0.001 to 30 mass ppm of organic impurities having a boiling point of 300 ° C. or higher with respect to the total mass of the treatment liquid.
[13] The treatment liquid contains at least one element selected from the group consisting of Fe, Cr, Ni and Pb, and the content of each element is 0.001 to 100 mass with respect to the total mass of the treatment liquid. The pattern forming method according to any one of [1] to [12], which is ppt.
[14] The treatment liquid contains at least one element selected from the group consisting of Fe, Cr, Ni and Pb, and the total amount of the elements is 0.001 to 100 mass ppt with respect to the total mass of the treatment liquid. The pattern forming method according to any one of [1] to [13].
[15] A treatment liquid used in the pattern forming method according to any one of [1] to [14], which contains 2 or more organic solvents having an ^{SP value of 16.3 MPa 1/2 or more, and the above 2} Of the above organic solvents, at least one is a treatment liquid having an ^{SP value of 17 to 18.2 MPa 1/2.}
[16] The treatment liquid according to [15] used for developing an exposed film.
[17] The treatment liquid according to [15] used for rinsing the developed film.
[18] The treatment liquid according to any one of [15] to [17], which contains 0.001 to 30 mass ppm of organic impurities having a boiling point of 300 ° C. or higher with respect to the total mass of the treatment liquid.
[19] The content of each element containing at least one 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. The treatment liquid according to any one of [15] to [18].
[20] The treatment liquid contains at least one element selected from the group consisting of Fe, Cr, Ni and Pb, and the total amount of the elements is 0.001 to 100 mass ppt with respect to the total mass of the treatment liquid. The treatment liquid according to any one of [15] to [19].
[21] The treatment liquid according to any one of [15] to [20], wherein the treatment liquid is produced through a distillation and / or filtration step.

According to the present invention, it is possible to provide a treatment liquid and a pattern forming method for resist film patterning that can simultaneously suppress the generation of defects on the resist and improve the resist LWR performance.

It is the schematic of the purification apparatus of the organic solvent used in the Example column.

[Treatment liquid]
The treatment liquid of the present invention is a treatment liquid for patterning a resist film containing an organic solvent. The treatment liquid of the present invention is preferably used to perform at least one of development and washing on a resist film obtained from a sensitive light beam or a radiation-sensitive composition (hereinafter, also referred to as “resist composition”). .. The treatment liquid of the present invention ^{contains two or more organic solvents having an SP value of 16.3 MPa 1/2} or more, and at least one of the two or more organic solvents has an SP value of 17 to 18.2 MPa ^1/2 . is there.
According to the treatment liquid of the present invention, it is possible to suppress the occurrence of defects on the resist and improve the resist LWR performance at the same time. The details of the reason have not been clarified yet, but it is speculated as follows.

In general, it is known that a poorly soluble component contained in a resist becomes a residue or a defect when it is not sufficiently removed by a developing or rinsing step. In order to efficiently remove such sparingly soluble components, it is necessary for a developing solution or a rinsing solution to solvate these components and diffuse them into the treatment liquid. In this process, a treatment liquid containing 2 or more organic solvents having an SP value of 16.3 MPa ^1/2 or more and at least one of the 2 or more organic solvents having an SP value of 17 to 18.2 MPa ^{1/2 is used.} When used, the poorly soluble component can be effectively removed by efficiently solvating the multiple parts having different polarities existing in the poorly soluble component with the parts having high affinity with each of the mixed solvents. It is presumed that the occurrence of defects on the resist can be suppressed.

On the other hand, if the affinity between the resist pattern and the developing solution is too low, the convection of the developing solution flowing through the resist pattern becomes non-uniform, causing microscopic development variations, and there is a concern that the LWR performance may deteriorate. On the other hand, ^{an organic solvent containing 2 or more organic solvents having an SP value of 16.3 MPa 1/2} or more and at least one of the 2 or more organic solvents having an SP value of 17 to 18.2 MPa ^1/2 is used. When mixed, it is presumed that the LWR performance was improved because the development became smooth with high affinity with the resist pattern.

As described above, by containing at least two kinds of organic solvents having a specific SP value as the treatment liquid, it is possible to suppress the occurrence of defects on the resist and improve the resist LWR performance at the same time.

The SP value of the present invention was calculated using the Fedors method described in "Properties of Polymers, 2nd Edition, 1976 Publishing". The formula used and the parameters of each substituent are shown below. The unit of the SP value is MPa ^1/2 unless otherwise specified.
SP value (Fedors method) = [(sum of aggregation energy of each substituent) / (sum of volume of each substituent)] ^0.5

The treatment liquid of the present invention is preferably used as a developer and / or a rinse liquid. The treatment liquid contains an organic solvent and may further contain an antioxidant and / or a surfactant.
Hereinafter, the organic solvent will be described first, and then the antioxidants and surfactants that may be contained in the treatment liquid will be described.

Hereinafter, organic solvents that can be used as organic solvents will be exemplified, but the present invention is not limited thereto. The numbers in parentheses indicate the SP value.

Examples of the ester solvent include methyl acetate (18.0), ethyl acetate (17.9), butyl acetate (17.8), isobutyl acetate (17.4), and amyl acetate (pentyl acetate) (17.8). ), propyl acetate (17.8), isopropyl acetate (17.4), isoamyl acetate (isopentyl acetate, 3-methylbutyl acetate) (17.4), 2-methylbutyl acetate (17.4), 1-methylbutyl acetate (17.4) 17.4), hexyl acetate (17.8), heptyl acetate (17.7), octyl acetate (17.7), ethyl methoxyacetate (18.3), ethyl ethoxyacetate (18.2), propylene glycol monomethyl Ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane) (17.9), ethylene glycol monoethyl ether acetate (18.2), ethylene glycol monopropyl ether acetate (18.2), ethylene glycol monobutyl ether acetate (18.1), ethylene glycol monophenyl ether acetate (18.4), diethylene glycol monomethyl ether acetate (18.5), diethylene glycol monopropyl ether acetate (18.4), diethylene glycol monoethyl ether acetate (18.4), Diethylene glycol monophenyl ether acetate (20.4), diethylene glycol monobutyl ether acetate (18.3), 2-methoxybutyl acetate (17.8), 3-methoxybutyl acetate (17.8), 4-methoxybutyl acetate (18) .2), 3-Methyl-3-methoxybutyl acetate (17.5), 3-ethyl-3-methoxybutyl acetate (18.1), propylene glycol monoethyl ether acetate (17.8), propylene glycol monopropyl Ether acetate (17.8), 2-ethoxybutyl acetate (17.8), 4-ethoxybutyl acetate (18.1), 4-propoxybutyl acetate (18.1), 2-methoxypentyl acetate (17.8) ), 3-methoxypentyl acetate (17.8), 4-methoxypentyl acetate (17.8), propylene glycol diacetate (19.6), methyl formate (21.0), ethyl formate (20.2), Butyl silicate (19.4), propyl silicate (19.7), ethyl lactate (24.4), butyl lactate (23.0), lactic acid Propyl (23.6), ethylmethyl carbonate (18.5), methylpropyl carbonate (18.3), methyl butyl carbonate (18.2), methyl pyruvate (21.6), ethyl pyruvate (21.1) , Propyl pyruvate (20.7), butyl pyruvate (20.3), methyl acetoacetate (21.1), ethyl acetoacetate (20.7), methyl propionate (17.9), ethyl propionate (17.9) 17.8), propyl propionate (17.8), isopropyl propionate (17.4), butyl propionate (17.8), pentyl propionate (17.8), hexyl propionate (17.7), Heptyl propionate (17.7), butyl butyl (17.8), isopropyl butano (17.4), isobutyl butyl (17.4), pentyl butyl (17.7), hexyl butano (17) .7), propyl pentanate (17.8), isopropyl pentanate (17.4), butyl pentanate (17.7), pentyl pentanate (17.7), ethyl hexanoate (17.8), hexane Propyl acid (17.7), butyl hexanoate (17.7), isobutyl hexanoate (17.5), methyl heptate (17.8), ethyl heptate (17.7), propyl heptate (17. 7), cyclohexyl acetate (19.7), cycloheptyl acetate (19.5), 2-ethylhexyl acetate (17.5), cyclopentyl propionate (26.3), and the like.
Among these, butyl acetate (17.8), amyl acetate (17.8), isoamyl acetate (17.4), 2-methylbutyl acetate (17.4), 1-methylbutyl acetate (17.4), hexyl acetate (17.8), Pentyl Propionate (17.8), Hexyl Propionate (17.7), Heptyl Propionate (17.7), Butyl Butate (17.8), Isobutyl Isobutate (17.1) Is preferably used, and isoamyl acetate (17.4) is particularly preferably used.

Examples of the ketone solvent include 2-octanone (18.0), 3-octanone (18.0), 4-octanone (18.0), 2-nonanonone (18.0), and 3-nonanonone (18. 0), 4-nonanonone (18.0), 5-nonanonone (18.0), acetone (18.6), 2-heptanone (18.1), 3-heptanone (18.1), 4-heptanone ( 18.1), 2-hexanone (18.2), 3-hexanone (18.2), diisobutyl ketone (17.4), diisopentyl ketone (17.4), diisohexyl ketone (17.4) , Diisoheptyl Ketone (17.4), Ethyl Isobutyl Ketone (17.7), Methyl Isopentyl Ketone (17.7), Ethyl Isopentyl Ketone (17.7), Procyl Isopentyl Ketone (17.7), Propylisobutylketone (17.7), 3-methyl-2-butanone (17.8), 3,3-dimethyl-2-butanone (17.3), cyclohexanone (20.0), cyclopentanone (20. 5), 3-Methylcyclohexanone (19.4), 4-methylcyclohexanone (19.4), phenylacetone (21.2), methylethylketone (18.4), methylisobutylketone (17.8), acetylacetone (21) .7), acetonyl acetone (21.2), diacetonyl alcohol (23.9), acetylmethylcarbinol (26.3), acetophenone (21.6), isophorone (17.6), propylene carbonate ( 23.6), γ-butyrolactone (23.8), methyl isoamyl ketone (17.5) and the like can be mentioned.
Among them, from the viewpoint of more excellent effect of the present invention, an acyclic ketone solvent (acyclic ketone) is preferable, and methyl isoamyl ketone (17.5), methyl isobutyl ketone (17.8), and 2-octanone (18. 0), 3-octanone (18.0), 4-octanone (18.0), 2-nonanonone (18.0), 3-nonanonone (18.0), 4-nonanonone (18.0), 5- Nonanone (18.0), 2-Heptanone (18.1), 3-Heptanone (18.1), 4-Heptanone (18.1), Diisobutyl Ketone (17.4), Diisopentyl Ketone (17.4) ), Diisohexyl ketone (17.4), diisoheptyl ketone (17.4) are more preferable, diisobutyl ketone (17.4), diisopentyl ketone (17.4), diisohexyl ketone (17. 4), diisoheptyl ketone (17.4), 4-heptanone (18.1), 5-nonanone (18.0) are more preferred, methylisoamylketone (17.5), methylisobutylketone (17.8). ), Diisobutylketone (17.4) and 2-heptanone (18.1) are particularly preferred.

Examples of alcohol-based solvents include methanol (28.2), ethanol (25.7), 1-propanol (24.2), isopropanol (23.7), 1-butanol (23.2), and 2-butanol. (22.7), 3-methyl-1-butanol (22.0), tert-butyl alcohol (22.3), 1-pentanol (22.4), 2-pentanol (22.0), 1 -Hexanol (21.9), 1-heptanol (21.4), 1-octanol (21.0), 1-decanol (20.5), 2-hexanol (21.5), 2-heptanol (21. 1), 2-octanol (20.7), 3-hexanol (21.5), 3-heptanol (21.1), 3-octanol (20.7), 4-octanol (20.7), 3- Methyl-3-pentanol (21.2), cyclopentanol (24.5), 2,3-dimethyl-2-butanol (20.8), 3,3-dimethyl-2-butanol (20.8) , 2-Methyl-2-pentanol (21.2), 2-Methyl-3-pentanol (20.1), 3-Methyl-2-pentanol (20.1), 3-Methyl-3-pen Tanol (21.2), 4-methyl-2-pentanol (21.2), cyclohexanol (23.6), 5-methyl-2-hexanol (20.8), 4-methyl-2-hexanol ( 20.8), 4,5-dimethyl-2-hexanol (20.2), 6-methyl-2-heptanol (20.5), 7-methyl-2-octanol (20.2), 8-methyl- Alcohols (monovalent alcohols) such as 2-nonanol (20.0), 9-methyl-2-decanol (19.8), 3-methoxy-1-butanol (22.3);
Glycol-based solvents such as ethylene glycol (36.5), diethylene glycol (30.6), and triethylene glycol (27.8);
Ethylene glycol monomethyl ether (24.5), propylene glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol) (23.0), diethylene glycol monomethyl ether (23.0), triethylene glycol monoethyl ether (21. 7), 3-methoxy3-methylbutanol (21.5), ethylene glycol monoethyl ether (23.5), ethylene glycol monopropyl ether (22.7), ethylene glycol monobutyl ether (22.1), propylene glycol Glycol ether-based solvent containing hydroxyl groups such as monoethyl ether (22.3), propylene glycol monopropyl ether (21.8), propylene glycol monobutyl ether (21.4), and propylene glycol monophenyl ether (24.2). ; Etc. can be mentioned.
Among these, it is preferable to use a glycol ether solvent.

Examples of the ether solvent include aromatic ether solvents such as anisole (19.2) and phenetol (19.0);
Examples thereof include alicyclic ether solvents such as tetrahydrofuran (18.4), tetrahydropyran (18.2) and 1,4-dioxane. Among these, it is preferable to use a glycol ether solvent or an aromatic ether solvent such as anisole.

Examples of the amide solvent include N-methyl-2-pyrrolidone (22.2), N, N-dimethylacetamide (18.7), N, N-dimethylpropioamide (18.5), N, N. -Dimethylformamide (21.2) or the like can be used.

Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents such as cyclohexane (17.5), cycloheptane (17.5), and cyclooctane (17.5);
Toluene (18.7), xylene (18.6), ethylbenzene (18.5), propylbenzene (18.4), 1-methyl-4-propylbenzene (18.4), diethylbenzene (18.4), Examples thereof include aromatic hydrocarbon-based solvents such as trimethylbenzene (18.6).

Of the organic solvents having an SP value of 16.3 MPa ^1/2 or more contained in the treatment liquid, at least one organic solvent having an SP value of 17 to 18.2 MPa ^1/2 (hereinafter, also referred to as a first solvent). ) Is not particularly limited, but the content of the organic solvent having an SP value of 17 to 18.2 MPa ^1/2 is usually 10 to 95% by mass, preferably 10 to 95% by mass, based on the total mass of the treatment liquid. Is 20 to 95% by mass, more preferably 30 to 80% by mass, and even more preferably 50 to 80% by mass.
Say Also, among the two or more SP value 16.3MPa ^1/2 or more organic solvent contained in the treatment liquid, an organic solvent SP value is not 17~18.2MPa ^1/2 (hereinafter, also a second solvent ) Is usually 5 to 95% by mass, preferably 10 to 70% by mass, and more preferably 10 to 60% by mass with respect to the total mass of the treatment liquid.
^{Of the organic solvents with an SP value of 16.3 MPa 1/2} or more contained in the treatment liquid, an organic solvent with an SP value of 17 to 18.2 MPa ^{1/2 and} an organic solvent with an SP value of 17 to 18.2 MPa ^{1 / The mass ratio with the organic solvent other than 2} (first solvent / second solvent) is not particularly limited, but is preferably 0.25 to 9, and more preferably 0.4 to 3.
^{Of the organic solvents having an SP value of 16.3 MPa 1/2} or more contained in the treatment liquid, the preferred SP value of the organic solvent having an SP value of 17 to 18.2 MPa ^{1/2 is 17.4 to} 18.1 is preferable, and 17.8 to 18.1 is more preferable. Of the organic solvents having an SP value of 16.3 ^{MPa 1/2} or more contained in the treatment liquid, the lower limit of the preferable SP value of the organic solvent whose SP value is not ^{17 to 18.2 MPa 1/2 is 20.} The above is preferable, and 23 or more is more preferable. ^{Of the organic solvents having an SP value of 16.3 MPa 1/2} or more contained in the treatment liquid, the upper limit of the organic solvent having an SP value of 17 to 18.2 MPa ^{not 1/2} is preferably 30 or less. 27 or less is more preferable.
The preferable combination of the solvent to be combined with the organic solvent having an SP value of 17 to 18.2 MPa ^{1/2 in the treatment liquid is not limited, but is not limited to the organic solvent having an SP value of 17 to 18.2 MPa 1/2} and the SP value. There combination of organic solvent 20 to 30 MPa ^1/2, SP value organic solvent and the SP value of 17～18.2MPa ^1/2 a combination of organic solvents 17～18.2MPa ^1/2 preferably, SP A combination of an organic solvent having a value of 17 to 18.2 MPa ^{1/2 and} an organic solvent having an SP value of 20 to 30 MPa ^{1/2 is more preferable.} A preferred combination is a mixture of γ-butyl lactone and butyl acetate.

<Developer and rinse solution that can be used in combination with the treatment solution>
Hereinafter, the developing solution and the rinsing solution that can be used in combination with the treatment liquid of the present invention will be described in detail.
The developer that can be used in combination with the treatment liquid of the present invention will be described in detail.
The developer has 6 or more carbon atoms (preferably 6 to 14) from the viewpoint of suppressing swelling of the resist film when EUV light (Extreme Ultra Violet) and EB (Electron Beam) are used in the exposure step described later. 6 to 12 is more preferable, and 6 to 10 is more preferable), and it is preferable to use an ester-based solvent having 2 or less heteroatoms.
The hetero atom of the ester-based 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.
Preferable examples of ester-based solvents having 6 or more carbon atoms and 2 or less heteroatomic atoms are 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 isobutate, and isoamyl acetate or butyl isobutate is particularly preferable.

When EUV light (Extreme Ultra Violet) and EB (Electron Beam) are used as the developing solution in the exposure step described later, instead of the above-mentioned ester solvent having 6 or more carbon atoms and 2 or less heteroatomic atoms, the developing solution is used. A mixed solvent of the ester solvent and the hydrocarbon solvent, 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.

As the organic solvent used as the developing solution, an ester solvent can be preferably mentioned. As the ester solvent, it is more preferable to use a solvent represented by the general formula (S1) described later or a solvent represented by the general formula (S2) described later, and a solvent represented by the general formula (S1) is used. Even more preferably, alkyl acetate is particularly preferable, and butyl acetate, amyl acetate (pentyl acetate), and isoamyl acetate (isoamyl acetate) are most preferable.

R ^0- C (= O) -OR ¹ General formula (S1)

In the general formula (S1), R ⁰ and R ¹ independently represent 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 be combined with each other to form a ring.
The ^{number of carbon atoms 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 number of carbon atoms of the cycloalkyl group is preferably 3 to 15.
R ⁰ and preferably a hydrogen atom or an alkyl group as R ^1, an alkyl groups for R ⁰ and R ^1, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, and the ring R and R 'and is formed by bonding the May be substituted with a hydroxyl group, a group containing a carbonyl group (for example, an acyl group, an aldehyde group, an 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 thereof include isopropyl acid acid, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate and the like.

Among these, ^{it is preferable that R 0} and R ¹ are unsubstituted alkyl groups.
The solvent represented by the general formula (S1) is preferably alkyl acetate, more preferably butyl acetate, amyl acetate (pentyl acetate), isoamyl acetate (isoamyl acetate), and isoamyl acetate. More preferred.

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

As the organic solvent used as the developing solution, 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 General formula (S2)

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

^{The alkylene group for R 3} in the general formula (S2) 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, and 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-methoxypropionate, 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 Acetates, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate and the like can be mentioned. Therefore, it is preferably propylene glycol monomethyl ether acetate.
Among these, ^{it is preferable that R 2} and R ⁴ are an unsubstituted alkyl group, R ³ is 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 methyl groups.

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

Further, as the organic solvent used as the developing solution, an ether solvent can also be preferably mentioned.
Examples of the ether solvent that can be used include the above-mentioned ether solvents. Among them, the ether solvent containing one or more aromatic rings is preferable, and the solvent represented by the following general formula (S3) is more preferable. , Most preferably anisole.

In the general formula (S3)
_RS 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 the organic solvent contained in the developing solution, the organic solvent used for the sensitive light ray or the radiation-sensitive composition described later can also be used.

The rinse liquid that can be used in combination with the treatment liquid of the present invention will be described in detail.
As the organic solvent contained in the rinsing solution, at least one selected from the group consisting of the ester solvent and the ketone solvent may be used from the viewpoint of being particularly effective in reducing the residue after development. Good.
When the rinsing solution 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, It is preferable to contain at least one solvent selected from the group consisting of ethyl-3-ethoxypropionate) and 2-heptanone as a main component, and at least selected from the group consisting of butyl acetate and 2-heptanone. It is particularly preferable to contain one kind of solvent as a main component.
When the rinsing solution contains at least one selected from the group consisting of an ester solvent and a ketone solvent, it is selected from the group consisting of an ester solvent, a glycol ether solvent, a ketone solvent, and an alcohol solvent. It is preferable to contain a solvent as a subcomponent, among which 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 preferable.
Among these, when an ester solvent is used as the organic solvent, it is preferable to use two or more kinds of ester solvents from the viewpoint that the above effects are 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 sub component. 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 (1 type or 2 or more types) from the viewpoint that the above effects are 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 sub component.
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 (1 type or 2 or more types) from the viewpoint that the above effects are further exhibited. You may. As a specific example in this case, a ketone solvent (preferably 2-heptanone) is used 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)) may be used as a subcomponent.
Here, the above-mentioned "main component" means that the content of the organic solvent with respect to the total mass is 50 to 100% by mass, preferably 70 to 100% by mass, and more preferably 80 to 100% by mass. It is more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass.
When a sub-component is contained, the content of the sub-component is preferably 0.1 to 20% by mass, preferably 0.5 to 10% by mass, based on the total mass (100% by mass) of the main component. It is more preferably mass%, and even more preferably 1-5 mass%.

A plurality of organic solvents may be mixed, or may be mixed and used with an organic solvent other than the above. The solvent may be mixed with water, but the water content in the rinsing solution is usually 60% by mass or less, preferably 30% by mass or less, more preferably 10% by mass or less, and most preferably 5% by mass or less. is there. By setting the water content to 60% by mass or less, good rinsing characteristics can be obtained.

Hereinafter, various additives that can be contained in the treatment liquid of the present invention will be described in detail. Of course, the following various additives may be contained in a developing solution and / or a rinsing solution that can be used in combination with the above-mentioned treatment solution of the present invention.
<Surfactant>
The treatment liquid may contain a surfactant. As a result, the wettability to the resist film is improved, and development and / or rinsing proceeds more effectively.
As the surfactant, the same surfactant as that used in the sensitive light ray or radiation-sensitive composition described later can be used.
The content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total mass of the treatment liquid. ..

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 at least one surfactant selected from the group consisting of anionic surfactants, nonionic surfactants and cationic surfactants as the surfactants. The wettability to the resist film is improved, and development and / or rinsing proceeds more effectively.

The surfactant may be contained in combination of two or more.

[2-1] Anionic Surfactants Examples of anionic surfactants include alkyl sulfate esters, alkyl sulfonic acids, alkyl benzene sulfonic acids, alkyl naphthalene sulfonic acids, alkyl diphenyl ether sulfonic acids, polyoxyethylene alkyl ether carboxylic acids, and polyoxyethylene. Examples thereof 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 ester, polyoxyethylene aryl ether sulfuric acid, and polyoxyethylene alkyl ether sulfuric acid are preferable, and polyoxyethylene aryl ether sulfuric acid is more preferable.

[2-2] Nonionic Surfactant The nonionic surfactant is, for example, a polyalkylene oxide alkylphenyl ether-based surfactant, a polyalkylene oxide alkyl ether-based surfactant, and a block polymer-based surfactant composed of polyethylene oxide and polypropylene oxide. Examples thereof include activators, polyoxyalkylene distyrene phenyl ether-based surfactants, polyalkylene tribenzyl phenyl ether-based surfactants, and acetylene polyalkylene oxide-based surfactants.

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

The quaternary ammonium salt-based surfactant includes, for example, tetramethylammonium chloride, tetrabutylammonium chloride, dodecyldimethylbenzylammonium chloride, alkyltrimethylammonium chloride, octyltrimethylammonium chloride, decyltrimethylammonium chloride, dodecyltrimethylammonium chloride, chloride. Examples thereof include tetradecyltrimethylammonium, cetyltrimethylammonium chloride, and stearyltrimethylammonium chloride. The quaternary ammonium salt-based surfactant is not particularly limited, but dodecyldimethylbenzylammonium chloride is preferable.

<Antioxidant>
The treatment liquid may contain an antioxidant. Thereby, the generation of the oxidizing agent over time can be suppressed.

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 the amine-based antioxidant include 1-naphthylamine, phenyl-1-naphthylamine, p-octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, p-dodecylphenyl-1-naphthylamine, and phenyl-2. Naphthylamine-based 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 Phenylenediamine antioxidants such as'-phenyl-p-phenylenediamine, dioctyl-p-phenylenediamine, 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'-didodecyldiphenylamine, p, p'-dystyryldiphenylamine, p, p'-dimethoxydiphenylamine, 4,4'-bis (4-α, α-dimethylbenzoyl) diphenylamine , P-Isopropoxydiphenylamine, diphenylamine-based antioxidants such as dipyridylamine; phenothiazine-based antioxidants such as phenothiazine, N-methylphenothiazine, N-ethylphenothiazine, 3,7-dioctylphenothiazine, phenothiazine carboxylic acid ester, phenoselenazine. Agents can be mentioned.
Examples of the phenolic antioxidant include 2,6-di-tershaributylphenol (hereinafter, tertiarybutyl is abbreviated as t-butyl) and 2,6-di-t-butyl-p-cresol. , 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,4-dimethyl-6-t-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-t-butylphenol), 2,2'-Methylenebis (4-ethyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol) , 4,4'-isopropyridenebis (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-methyl Phenol, 3-t-butyl-4-hydroxyanisole, 2-t-butyl-4-hydroxyanisole, octyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- (4) Stearyl-hydroxy-3,5-di-t-butylphenyl) propionate, oleyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- (4-hydroxy-3,5) Dodecyl -di-t-butylphenyl) propionate, decyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- (4-hydroxy-3,5-di-t-butyl) Octyl propionate, tetrakis {3- (4-hydroxy-3,5-di-t-butylphenyl) propionyloxymethyl} methane, 3- (4-hydroxy-3,5-di-t-butylphenyl) Propionic acid glycerin monoester, 3- (4-hydroxy-3,5-di-t-butylphenyl) ester of propionic acid with glycerin monooleyl ether, 3- (4-hydroxy-3,5-di-t-) Butylphenyl) propionic acid butylene glycol diester, 2,6-di-t-butyl-α-dimethy Luamino-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-hydrocinamide), 3,9-bis [1,1-dimethyl-2-{β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8, 10-Tetraoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4-hydroxy-5-t-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, etc. Can be mentioned.

The content of the antioxidant is not particularly limited, but is preferably 0.0001 to 1% by mass, more preferably 0.0001 to 0.1% by mass, and 0.0001 to 0, based on the total mass of the treatment liquid. 0.01% by mass is more preferable. When it is 0.0001% by mass or more, a more excellent antioxidant effect is obtained, and when it is 1% by mass or less, the residue after development and rinsing tends to be suppressed.

<Basic compound>
The treatment liquid of the present invention can 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 cheilitis or radiation-sensitive composition described later.
Among the basic compounds that can be contained in the treatment liquid of the present invention, nitrogen-containing compounds can be preferably used.

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

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

In the above formula (1), R ¹ and R ² are 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, and 3 to 30 carbon atoms. It is an alicyclic hydrocarbon group of 30, 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, and the like. It is 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 chain hydrocarbon group having 1 to 30 carbon atoms 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. Groups, 1-methylpropyl groups, t-butyl groups and the like can be mentioned.

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, a norbonyl group and the like.

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 an aralkyl group having 6 to 12 carbon atoms such as a benzyl group, a phenethyl group, a naphthylmethyl group and a naphthylethyl group. Can be mentioned.

The n-valent chain hydrocarbon group having 1 to 30 carbon atoms represented by ^{R 3} is, for example, the group exemplified as the chain hydrocarbon group having 1 to 30 carbon atoms represented by ^{R 1} and R ^2. Examples thereof include a group obtained by removing (n-1) hydrogen atoms from the same group as described above.

The aliphatic cyclic hydrocarbon group having 3 to 30 carbon atoms represented by ^{R 3} is a group similar to the group exemplified as the cyclic hydrocarbon group having 3 to 30 carbon atoms represented by ^{R 1} and R ^{2, for example.} Examples thereof include a group obtained by removing (n-1) hydrogen atoms from the group.

The aromatic hydrocarbon group having 6 to 14 carbon atoms represented by ^{R 3} is the same as the group exemplified as the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by ^{R 1} and R ^{2, for example.} Examples thereof include 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, for example.} Examples thereof include 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, an alkoxy group and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like.

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 the (cyclo) alkylamine compound include a compound having one nitrogen atom, a compound having two nitrogen atoms, and a compound having three or more nitrogen atoms.

Examples of the (cyclo) alkylamine compound having one nitrogen atom include mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, 1-aminodecane, and cyclohexylamine. 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 Tri (cyclo) alkylamines such as -n-octylamine, tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, methyldicyclohexylamine, tricyclohexylamine; substituted alkylamines such as triethanolamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 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-) Examples include aromatic amines such as aminophenyl) -2- (4-hydroxyphenyl) propane.

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 ( Examples thereof include 2-diethylaminoethyl) ether, 1- (2-hydroxyethyl) -2-imidazolidinone, 2-quinoxalinol, 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 a nitrogen-containing aromatic heterocyclic compound and a nitrogen-containing aliphatic heterocyclic compound.

Examples of the nitrogen-containing aromatic heterocyclic compound include imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, 1-benzyl-2-methylimidazole and 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-hydroxyquinolin, 8-oxyquinoline, aclydin, 2,2': 6', 2''-terpyridine and the like.

Examples of the nitrogen-containing aliphatic heterocyclic compound include piperazines 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 thereof 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, and 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, N-t-Butoxycarbonyl-4-hydroxypiperidine, Nt-butoxycarbonylpyrrolidine, Nt-butoxycarbonylpiperazine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantyl Amin, Nt-butoxycarbonyl-4,4'-diaminodiphenylmethane, N, N'-di-t-butoxycarbonylhexamethylenediamine, N, N, N', N'-tetra-t-butoxycarbonylhexamethylene Diamine, N, N'-di-t-butoxycarbonyl-1,7-diaminoheptane, N, N'-di-t-butoxycarbonyl-1,8-diaminooctane, N, N'-di-t-butoxy Carbonyl-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, N-t-butoxycarbonylbenzimidazole, N-t-butoxycarbonyl-2-methylbenzimidazole, N-t-butoxycarbonyl-2-phenylbenzimidazole Etc., N-t-butoxycarbonyl group-containing amino compounds; formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N- Examples thereof include methylpyrrolidone, N-acetyl-1-adamantylamine, tris isocyanurate (2-hydroxyethyl) and the like.

Examples of the urea compound include urea, methyl urea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, and the like.

Among the above-mentioned nitrogen-containing compounds, a nitrogen-containing compound having an SP value of 18 or less is preferably used from the viewpoint of suppressing development defects. This is because the nitrogen-containing compound having an SP value of 18 or less has a good affinity with the rinsing liquid used in the rinsing process described later, and can suppress the occurrence of development defects such as precipitation.

(Cyclo) alkylamine compounds and nitrogen-containing aliphatic heterocyclic compounds that satisfy the above-mentioned conditions (SP value) are preferable, and 1-aminodecane, di-n-octylamine, tri-n-octylamine, and tetramethylethylenediamine are preferable. More preferred. The table below shows the SP values and the like of these nitrogen-containing aliphatic heterocyclic compounds.

The content of the basic compound (preferably nitrogen-containing compound) in the treatment liquid is not particularly limited, but is preferably 10% by mass or less based on the total amount of the treatment liquid in that the effect of the present invention is more excellent. 5 to 5% by mass is preferable.
In the present invention, only one type of the above nitrogen-containing compound may be used, or two or more types having different chemical structures may be used in combination.

The above-mentioned treatment liquid can also be suitably applied to a non-chemically amplified resist.
Examples of the non-chemical amplification type resist include the following.
(1) A resist material whose main chain is cleaved by irradiation with g-line, h-line, i-line, KrF, ArF, EB, EUV, etc. and whose solubility changes as the molecular weight decreases (for example, Japanese Patent Application Laid-Open No. 2013-210411). The main component is a copolymer of an α-chloroacrylic acid ester compound and an α-methylstyrene compound described in paragraphs 0025 to 0029 and 0056 of Japanese Patent Application Laid-Open No. 2015/0008211 and paragraphs 0032 to 0036 and 0063 of US Patent Publication 2015/0008211. Resist material, etc.) (2) Resist material such as hydrogen silcesoxane (HSQ) with silanol condensation reaction generated by g-line, h-line, i-line, KrF, ArF, EB, EUV, etc., and calixarene substituted with chlorine. (3) Metal complexes (magnesium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium) that absorb light such as g-line, h-line, i-line, KrF, ArF, EB or EUV. , Indium, tin, antimony, cesium, zirconium, hafnium, etc., and titanium, zirconium, hafnium are preferable from the viewpoint of pattern formation). Resists involving a position exchange process (paragraphs 0017 to 0033, 0037 to 0047 of JP2015-075500A, paragraphs 0017 to 0032, 0043 to 0044 of JP2012-185485A, paragraphs of US Patent Publication No. 2012/0208125). (Resist material described in 0042 to 0051, 0066, etc.) and the like.

Further, the above-mentioned treatment liquid can be suitably applied to a silicon-based resist.
Examples of the silicon-based resist include the resist materials described in paragraphs 0010 to 0062 and paragraphs 0129 to 0165 described in JP-A-2008-83384.

[Pattern formation method]
The pattern forming method of the present invention uses (a) a step of forming a resist film using a sensitive light beam or a radiation-sensitive composition, (b) a step of exposing the film, and (c) a treatment liquid. It includes a processing step of processing the exposed film.

Hereinafter, each step of the pattern forming method of the present invention will be described. Further, as an example of the processing process, each of the developing process and the rinsing process will be described.

<Resist film forming step (a)>
The resist film forming step is a step of forming a resist film using an actinic cheilitis or radiation-sensitive composition, and can be carried out by, for example, the following method.
In order to form a resist film (actinic cheilitis or radiation-sensitive composition film) on a substrate using an actinic cheilitis or radiation-sensitive composition, each component described later is dissolved in a solvent to cause activity. A light 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 micron or less, more preferably 0.05 micron or less, still more preferably 0.03 micron or less.

The actinic or radiation-sensitive composition is applied onto a substrate (eg, silicon, silicon dioxide coating) such as that used in the manufacture of integrated circuit devices by a suitable coating method such as a spinner. Then, it dries to form a resist film. If necessary, various undercoat films (inorganic film, organic film, antireflection film) 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 ordinary exposure and means provided in a 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., further 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, 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 film thickness of the resist film formed is preferably 50 nm or less. When the film thickness is 50 nm or less, pattern collapse is less likely to occur when the development step described later is applied, and more excellent resolution performance can be obtained.
The film thickness is more preferably in the range of 15 nm to 45 nm. When the film thickness is 15 nm or more, sufficient etching resistance can be obtained. The film thickness range is more preferably 15 nm to 40 nm. When the film thickness is in 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 upper layer of the resist film. The upper layer film can be formed by using, for example, a composition for forming an upper layer film 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 later.

<Exposure step (b)>
The exposure step is a step of exposing the resist film, and can be performed by, for example, the following method.
The resist film formed as described above is irradiated with active light rays or radiation through a predetermined mask. In the irradiation of the electron beam, drawing (direct drawing) without using a mask is common.
The active light or radiation is not particularly limited, and examples thereof include KrF excimer laser, ArF excimer laser, EUV light (Extreme Ultra Violet), electron beam (EB, Electron Beam) and the like. The exposure may be immersion exposure.

<Bake>
In the pattern forming method of the present invention, it is preferable to bake (heat) after exposure and before developing. Baking accelerates the reaction of the exposed area, resulting in better sensitivity and pattern shape.
The heating temperature is preferably 80 to 150 ° C, more preferably 80 to 140 ° C, still more preferably 80 to 130 ° C.
The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, 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.

<Step (c) of treating the exposed film using the treatment liquid>
<< Development process >>
The developing step is a step of developing the exposed resist film with a developing solution.

Examples of the developing method include a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), and a method of developing by raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle). Method), a method of spraying the developer on the surface of the substrate (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic discharge method). Etc. can be applied.
Further, after the step of performing the development, a step of stopping the development may be carried out while substituting with another solvent.
The developing time is not particularly limited as long as the resin in the unexposed portion is sufficiently dissolved, and is usually 10 to 300 seconds, preferably 20 to 120 seconds.
The temperature of the developing solution is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.

As the developing solution used in the developing step, it is preferable to use the above-mentioned processing solution. The developer is as described above. In addition to development using a treatment liquid, 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 above-mentioned developing step.

In the rinsing step, the developed wafer is washed with the above rinsing solution.
The cleaning treatment method is not particularly limited, but for example, a method of continuously discharging the rinse liquid onto a substrate rotating at a constant speed (rotary discharge method), or a method of 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 rinse solution on the surface of the substrate (spray method), etc. can be applied. Among them, the cleaning treatment is performed by the rotary discharge method, and after cleaning, the substrate is rotated at a rotation speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate.
The rinsing 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 rinsing solution is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.

Further, after the developing treatment or the rinsing treatment, a treatment of removing the developing solution or the rinsing solution adhering to the pattern with a supercritical fluid can be performed.
Further, after the development treatment, the rinsing treatment, or the treatment with the supercritical fluid, a heat treatment can be performed 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, 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, preferably 15 to 180 seconds.

As the rinsing solution, it is preferable to use the above-mentioned treatment solution. The explanation of the rinsing liquid is as described above.

In the pattern forming method of the present invention, at least one of the developing solution and the rinsing solution is the above-mentioned treatment solution, but it is particularly preferable that the rinsing solution is the above-mentioned treatment solution.

Generally, the developer and the rinse liquid are stored in the waste liquid tank through a pipe after use. At that time, if a hydrocarbon solvent is used as the rinsing solution, the resist dissolved in the developing solution is deposited and adheres to the back surface of the wafer side or the side surface of the piping, which contaminates the apparatus.
In order to solve the above problem, there is a method of passing a solvent in which the resist dissolves through the pipe again. As a method of passing through the pipe, a method of cleaning the back surface and side surfaces of the substrate with a solvent in which the resist dissolves after cleaning with a rinse solution and flowing the substrate, or a method in which the solvent in which the resist dissolves without contacting the resist is passed through the pipe. There is a method of flowing.
The solvent to be passed through the pipe is not particularly limited as long as it can dissolve the resist, and examples thereof include the above-mentioned organic solvents, such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and 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 mono Ethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-heptanone, ethyl lactate, 1-propanol, acetone, and the like can be used. Of these, PGMEA, PGME, and cyclohexanone can be preferably used.

[Sensitive ray or radiation sensitive composition (resist composition)]
Next, a sensitive actinic 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 light-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, and at least (i) a repeating unit having a group that decomposes by the action of an acid to generate a carboxyl group (further). , May have a repeating unit having a phenolic hydroxyl group), or at least (ii) having a repeating unit having a phenolic hydroxyl group.
If it has a repeating unit that is decomposed by the action of an acid and has a carboxyl group, the solubility in an alkaline developer increases and the solubility in an organic solvent decreases due to the action of the acid.

Examples of the repeating unit having a phenolic hydroxyl group contained in the resin (A) include a repeating unit represented by the following general formula (I).

During the ceremony
R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₄₂ may _{be bonded to Ar 4} to form a ring, in which case R ₄₂ 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 represents an (n + 2) -valent aromatic ring group when combined with _{R 42 to form a ring.}
n represents an integer of 1 to 5.

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

_{The cycloalkyl groups of R 41} , R ₄₂ , and R ₄₃ in the general formula (I) may be monocyclic or polycyclic. Preferably, a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group which may have a substituent can be 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.
The alkyl group contained in the alkoxycarbonyl group _{of R 41} , R ₄₂ , and R ₄₃ in the general formula (I) is preferably the same as the alkyl group in _{R 41} , R ₄₂ , and R _43.

Preferred substituents in each of the above groups include, for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group and an acyl group. Examples thereof include a group, an asyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group 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 may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylen group, a naphthylene group, and an anthracenylene group, or an arylene group having 6 to 18 carbon atoms. For example, an aromatic ring group containing a heterocycle such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzoimidazole, triazole, thiadiazol, thiazole and the like can be mentioned as a preferable example.

As a specific example of the (n + 1) -valent aromatic ring group when n is an integer of 2 or more, (n-1) arbitrary hydrogen atoms are removed from the above-mentioned specific example of the divalent aromatic ring group. The group obtained from the above can be preferably mentioned.
The (n + 1) -valent aromatic ring group may further have a substituent.

Examples of the substituent that the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group and (n + 1) -valent aromatic ring group can have are R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I). Examples thereof include an alkoxy group such as an alkyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group and a butoxy group; an aryl group such as a phenyl group; 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 , Isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and other alkyl groups having 20 or less carbon atoms, more preferably alkyl groups having 8 or less carbon atoms. Can be mentioned.
As X ₄ , a single bond, -COO-, and -CONH- are preferable, and a single bond, -COO- is more preferable.

Examples _{of the alkylene group in L 4} include those having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and an octylene group which may have a substituent.
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 of the resin (A) is preferably a repeating unit represented by the following general formula (p1).

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

Ar in the general formula (p1) represents an aromatic ring, and may have a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, and a phenanthrene ring. A hydrogen ring or a heterocycle such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrol ring, a triazine ring, an imidazole ring, a benzoimidazole ring, a triazole ring, a thiadiazole ring, or a thiazole ring. Aromatic heterocycles containing can be mentioned. Of these, the benzene ring is the most preferable.

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

Hereinafter, specific examples of the repeating unit having the phenolic hydroxyl group of the resin (A) will be shown, but the present invention is not limited thereto. In the formula, a represents 1 or 2.

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

The repeating unit having a group that decomposes by the action of the acid of the resin (A) to generate a carboxyl group is a repeating unit having a group substituted with a group in which the hydrogen atom of the carboxyl group is decomposed by the action of the acid and eliminated. Is.

Examples of the groups eliminated by acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and -C (R ₀₁ ) (R _02). ) (OR ₃₉ ) and the like.
In the formula, R _{36 to} R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be combined with each other to form a ring.
R ₀₁ and R ₀₂ each independently represent 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 of the resin (A) which is decomposed by the action of an acid to generate a carboxyl group, a repeating unit represented by the following general formula (AI) is preferable.

In the general formula (AI)
Xa ₁ represents a hydrogen atom and an alkyl group which may have a substituent.
T represents a single bond or a divalent linking group.
Rx _{1 to Rx 3} independently represent 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), it is preferable that at least two of _{Rx 1 to Rx 3 are methyl groups.}
Two of Rx _{1 to Rx 3} may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

Represented by xa _1, as the alkyl group which may have a substituent group, include groups represented by methyl group or _-CH 2 _{-R 11.} R ₁₁ represents a halogen atom (fluorine atom or the like), 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. It is an alkyl group of, 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 of T include an alkylene group, an -COO-Rt- group, an -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, a − (CH ₂ ) ₂ − group, and a − (CH ₂ ) ₃ − group.

As _{the alkyl group of Rx 1 to Rx 3} , those having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a t-butyl group are preferable.
Examples of the cycloalkyl group of Rx _{1 to Rx 3} include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an 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, and an adamantyl group. Polycyclic cycloalkyl groups such as groups are 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 hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group. It may be replaced.
As the repeating unit represented by the general formula (AI), for example, it is preferable that Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-mentioned 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. Examples thereof include a carbonyl group (2 to 6 carbon atoms), preferably 8 or less carbon atoms.

The repeating unit represented by the general formula (AI) is preferably an acid-degradable (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. It is a repeating unit that represents. 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 It is a unit.

Specific examples of the repeating unit having a group of the resin (A) having a group which decomposes by the action of an acid to generate a carboxyl group are shown below, but the present invention is not limited thereto.
In the specific example, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and if there are a plurality of Z, they are independent of each other. 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, which is preferable. Is an alkyl group having a hydroxyl group. The isopropyl group is particularly preferable as the branched alkyl group.

The content of the repeating unit having a group that decomposes by the action of an acid to generate a carboxyl group is preferably 15 to 90 mol%, more preferably 20 to 90 mol%, based on all the repeating units in the resin (A). 25-80 mol% is even more preferable, and 30-70 mol% is even 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, and the 5- to 7-membered ring lactone structure has a bicyclo structure. It is preferable that the other ring structure is fused so as to form a spiro structure.
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. A preferable lactone structure is a group represented by the general formulas (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14).

The lactone structural 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-degradable group and the like. n2 represents an integer from 0 to 4. When n2 is 2 or more, Rb ₂ existing in plural numbers may be the same or different or may be bonded to form a ring Rb ₂ between the plurality of.

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 be done.

In the 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 of Rb ₀ may have include a hydroxyl group and a halogen atom.
Examples of the halogen atom of 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 divalent linking group having a single bond, an alkylene group, 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. Preferably, it is a single bond, a linking group represented by _{−Ab 1} −CO _2−. 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 norbornene group.
V represents a group represented by any 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. Further, one kind of 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 repeating units having a group having a lactone structure are given below, but the present invention is not limited thereto.

The content of the repeating unit having a lactone group is preferably 1 to 65 mol%, more preferably 1 to 30 mol%, still more preferably 5 to 25 mol%, based on all the repeating units in the resin (A). -20 mol% is even more preferred.
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 substrate adhesion and developer affinity. As the alicyclic hydrocarbon structure substituted with the polar group, an adamantyl group, a diamantyl group and a norbornane group are preferable. As the polar group, a hydroxyl group and a cyano group are preferable.
Specific examples of repeating units having a polar group are given 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 the repeating units in the resin (A). % Is more preferable, 5 to 25 mol% is further preferable, and 5 to 20 mol% is even more preferable.

Further, as the repeating unit other than the above, a repeating unit having a group that generates an acid by irradiation with active light or radiation (photoacid generating group) 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 by irradiation with active light 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 is decomposed by irradiation with active light or radiation to generate an acid in the side chain.

Hereinafter, specific examples of the repeating unit represented by the general formula (4) will be shown, but the present invention is not limited thereto.

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-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 the repeating units in the resin (A). , More preferably 5 to 35 mol%, still more preferably 5 to 30 mol%.

The resin (A) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a batch polymerization method in which a monomer seed and an initiator are dissolved in a solvent and polymerized by heating, or a solution of the monomer seed and the initiator is added dropwise to the heating solvent over 1 to 10 hours. 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; described later. Examples thereof include a solvent that dissolves a sensitive light-sensitive or radiation-sensitive composition such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone. More preferably, the polymerization is carried out using the same solvent as the solvent used for the actinic cheilitis or radiation-sensitive composition. As a result, the generation of particles during storage can be suppressed.

The polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon. As the polymerization initiator, a commercially available radical initiator (azo-based initiator, peroxide, etc.) is used to initiate polymerization. As the radical initiator, an azo-based initiator is preferable, and an azo-based initiator having an ester group, a cyano group, and a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after the reaction is completed, the desired polymer is recovered by a method such as powder or solid recovery by adding it to a solvent. The concentration of the reaction product is 5 to 50% by mass, preferably 10 to 30% by mass.
The reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., and more preferably 60 to 100 ° C.
Purification is a solution purification method such as a liquid-liquid extraction method that removes residual monomers and oligomer components by washing with water or a combination of appropriate solvents, and ultrafiltration that extracts and removes only those with a specific molecular weight or less. In a solid state, such as a reprecipitation method in which a resin solution is dropped into a poor solvent to solidify the resin in the poor solvent to remove residual monomers, or a filtered resin slurry is washed with a poor solvent. Ordinary methods such as the purification method of can be applied.

The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and most preferably 5,000 to 15, in terms of polystyrene by the GPC method. It is 000. By setting the weight average molecular weight to 1,000 to 200,000, it is possible to prevent deterioration of heat resistance and dry etching resistance, and the developability is deteriorated, the viscosity is increased, and the film forming property is deteriorated. It can be prevented from being etched.
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 the GPC method. By setting the weight average molecular weight to 3,000 to 9,500, a resist residue (hereinafter, also referred to as “scum”) is 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, and particularly preferably 1.2 to 2.0. .. The smaller the degree of dispersion, the better the resolution and resist shape, the smoother the side wall of the resist pattern, and the better the roughness.

In the actinic cheilitis 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.
Further, in the actinic cheilitis or radiation-sensitive composition, the resin (A) may be used alone or in combination of two or more.

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

In the 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, in which case R ₆₂ 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 combined with _{R 62 to form a ring.}
Y ₂ represents a group desorbed by the action of a hydrogen atom or an acid independently when n ≧ 2. However, _{at least one of Y 2} represents a group that is eliminated by the action of an acid.
n represents an integer of 1 to 4.
_{As the group Y 2} desorbed 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.
Q, M, of at least two members to the ring (preferably, 5-membered or 6-membered ring) L ₁ may be formed.

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 are 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 combined to form a ring.

The _{aromatic ring group represented by Ar 3 is the same as that of 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, and further. It is preferably a phenylene group.

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 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, in which case R ₄₂ represents an alkylene group.
L ₄ represents a single bond or a divalent linking group, and when 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 are, represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.
Q _4, at least two of _{M 4} and _{R 44} may combine with each other to form a ring.
R ₄₁ , R ₄₂ and R _{43 are synonymous with R 51} , R ₅₂ and R _{53 in} the above general formula (V), and the preferred range is also the same.
L _{4 has the same meaning as L 5} in the above-mentioned general formula (V), and the preferable range is also the same.
R ₄₄ and R _{45 are synonymous with R 3} in the above-mentioned general formula (3), and the preferable range is also the same.
M _{4 has the same meaning as M 3} in the above-mentioned general formula (3), and the preferable range is also the same.
Q ₄ are the same meaning as Q ₃ in the above general formula (3), 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 a ring formed by combining at least two of Q ₃ , M ₃ and R ₃ , and the preferred range is also the same. Is.
Specific examples of the repeating unit represented by the general formula (4) are shown below, but the present invention is not limited thereto.

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

In the 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 combined with 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 the present invention is not limited thereto.

The repeating unit having the acid-decomposable group may be one kind or a combination of two or more kinds.

The content of the repeating unit having an acid-degradable group in the resin (A) (the total when a plurality of types are contained) 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, and further preferably 10 mol% or more and 65 mol% or less.

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

During the ceremony
R ₆ and R ₇ are independently hydrogen atoms, hydroxy groups, linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, alkoxy groups or asyloxy groups, cyano groups, nitro groups, amino groups, respectively. It represents a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group.
n ₃ represents an integer from 0 to 6.
n ₄ represents an integer from 0 to 4.
X ⁴ is a methylene group, an oxygen atom or a sulfur atom.
Specific examples of the repeating unit represented by the general formula (V) or the general formula (VI) are shown below, but the present invention is not limited thereto.

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, a vinyl-based repeating unit having a silicon atom, and the like. 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, and examples of the group having a silicon atom include a trimethylsilyl group, a triethylsilyl group, and a triphenyl. Cyril group, tricyclohexylsilyl group, tristrimethylsiloxysilyl group, tristrimethylsilylsilyl group, methylbistrimethylsilylsilyl group, methylbistrimethylsiloxysilyl group, dimethyltrimethylsilylsilyl group, dimethyltrimethylsiloxysilyl group, or cyclic or cyclic group as described below. Examples thereof include a linear polysiloxane, a cage type, a ladder type, or a random type silsesquioxane structure. In the formula, R and R1 each independently represent a monovalent substituent. * Represents a bond.

As the repeating unit having the above group, for example, a repeating unit derived from an acrylate or methacrylate compound having the above group, or a repeating unit derived from a compound having the above group and a vinyl group can be preferably mentioned.

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 has a high aspect ratio (for example, a cross-sectional shape). In the formation of a pattern having a film thickness / line width of 3 or more), very excellent tilting performance can be exhibited.
Examples of the silsesquioxane structure include a cage-type silsesquioxane structure, a ladder-type silsesquioxane structure (ladder-type silsesquioxane structure), and a random-type silsesquioxane structure. Of these, a cage-type silsesquioxane structure is preferable.
Here, the cage-type silsesquioxane structure is a silsesquioxane structure having a cage-like skeleton. The cage-type silsesquioxane structure may be a complete cage-type silsesquioxane structure or an incomplete cage-type silsesquioxane structure, but the cage-type silsesquioxane structure may be a complete cage-type 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-type silsesquioxane structure is preferably a siloxane structure represented by the following formula (S).

In the above formula (S), R represents a monovalent organic group. The plurality of Rs may be the same or different.
The organic group is not particularly limited, and specific examples thereof include a hydroxy group, a nitro group, a carboxy group, an alkoxy group, an amino group, a mercapto group, and a blocked mercapto group (for example, a mercapto group blocked (protected) with an acyl group). ), Acrylic group, imide group, phosphino group, phosphinyl group, silyl group, vinyl group, hydrocarbon group which may have a hetero atom, (meth) acrylic group-containing group, epoxy group-containing group and the like.
Examples of the heteroatom of the hydrocarbon group which may have the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom and a phosphorus atom.
Examples of the hydrocarbon group of the hydrocarbon group which may have the heteroatom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these are combined.
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 1 to 30 carbon atoms), a linear or branched alkenyl group (particularly 2 to 30 carbon atoms), and the like. Examples thereof include a linear or branched alkynyl group (particularly, having 2 to 30 carbon atoms).
Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xsilyl group, and a naphthyl group.

When the resin (A) has a repeating unit having a silicon atom in the side chain, the content thereof is preferably 1 to 30 mol%, preferably 5 to 25 mol%, based on all the repeating units in the resin (A). Is even more preferable, and 5 to 20 mol% is even more preferable.

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

In the above general formula (ZI)
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent 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.
Further, 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, and a carbonyl group. Examples of the group formed by bonding two of R _{201 to} R ₂₀₃ include an alkylene group (for example, a butylene group and a pentylene group).
Z ⁻ represents a non-nucleophilic anion (anion with a significantly lower ability to undergo a nucleophilic reaction).

Examples of the non-nucleophilic anion include a sulfonic acid anion (aliphatic sulfonic acid anion, aromatic sulfonic acid anion, camphor sulfonic acid anion, etc.) and a carboxylic acid anion (aliphatic carboxylic acid anion, aromatic carboxylic acid anion, aralkyl. Carboxylic acid anion etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.

The aliphatic moiety in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid 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 of carbon atoms. Included are 3 to 30 cycloalkyl groups.

The aromatic group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion preferably includes an aryl group having 6 to 14 carbon atoms, for example, a phenyl group, a tolyl group, a naphthyl group and the like.

The alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples of this include halogen atoms such as nitro groups and fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), and cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), Aryl group (preferably 6 to 14 carbon atoms), alkoxycarbonyl group (preferably 2 to 7 carbon atoms), acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (preferably 1 to 15 carbon atoms), alkyliminosulfonyl group (preferably 1 to 15 carbon atoms), aryloxysulfonyl group (preferably carbon number). Number 6 to 20), alkylaryloxysulfonyl group (preferably 7 to 20 carbon atoms), cycloalkylaryloxysulfonyl group (preferably 10 to 20 carbon atoms), alkyloxyalkyloxy group (preferably 5 to 20 carbon atoms) ), Cycloalkylalkyloxyalkyloxy group (preferably 8 to 20 carbon atoms) and the like.
Regarding the aryl group and the ring structure of each group, an alkyl group (preferably having 1 to 15 carbon atoms) can be further mentioned as a substituent.

The aralkyl group in the aralkyl carboxylic acid anion preferably includes an aralkyl group having 7 to 12 carbon atoms, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylbutyl group and the like.

Examples of the sulfonylimide anion include a saccharin anion.

The alkyl group in the bis (alkylsulfonyl) imide anion and the tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of the substituent of these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, a cycloalkylaryloxysulfonyl group and the like. A fluorine atom or an alkyl group substituted with a fluorine atom is preferable.
Further, 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.

Other non-nucleophilic anions include, for example, phosphorus fluoride (eg, PF ₆ ⁻ ), boron fluoride (eg BF ₄ ⁻ ), antimony fluoride (eg SbF ₆ ⁻ ) and the like. ..

Examples of the non-nucleophilic anion include an aliphatic sulfonic acid anion in which at least the α position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonic acid anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group having a fluorine atom. Bis (alkylsulfonyl) imide anions substituted with, and tris (alkylsulfonyl) methide anions in which the alkyl group is substituted with a fluorine atom are preferable. As the non-nucleophilic anion, a perfluoroaliphatic sulfonic acid anion (more preferably 4 to 8 carbon atoms), a benzenesulfonic acid anion having a fluorine atom, and even more preferably a nonafluorobutane sulfonic acid anion, perfluoro Octane sulfonic acid anion, pentafluorobenzene sulfonic acid anion, 3,5-bis (trifluoromethyl) benzene sulfonic acid anion.

From the viewpoint of acid strength, it is preferable that the pKa of the generated acid is -1 or less in order to improve the sensitivity.

Further, as the non-nucleophilic anion, an anion represented by the following general formula (AN1) is also mentioned as a preferable embodiment.

During the ceremony
Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ¹ and R ² independently represent a hydrogen atom, a fluorine atom, or an alkyl group, and when a plurality of them are present, R ¹ and R ² may be the same or different from each other.
L represents a divalent linking group, and when a plurality of L are present, 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, and more preferably 1 to 4 carbon atoms. The alkyl group substituted with the fluorine atom of Xf is preferably a perfluoroalkyl group.
The Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include 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 , and among them, fluorine atom and CF ₃ are preferable.
In particular, it is preferable that both Xfs are fluorine atoms.

The alkyl groups of R ¹ and R ² may have a substituent (preferably a fluorine atom), and those having 1 to 4 carbon atoms are preferable. More preferably, it is a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of alkyl groups having R ¹ and R ² _{substituents 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 are mentioned, and CF ₃ is preferable.
R ¹ and R ² are preferably a fluorine atom or CF ₃ .

x is preferably 1 to 10, more preferably 1 to 5.
y is preferably 0 to 4, more preferably 0.
z is preferably 0 to 5, 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-, alkylene group, cycloalkylene group,} Examples thereof include an alkenylene group or a linking group in which a plurality of these groups are linked, and a linking group having a total carbon number of 12 or less is preferable. Of these, -COO-, -OCO-, -CO-, and -O- are preferable, and -COO- and -OCO- are more preferable.

In the general formula (ANI), 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- it is 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 an alicyclic group, an aryl group, or a heterocyclic group (not only those having aromaticity but also not having aromaticity). (Including those) 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 tetracyclododeca. A polycyclic cycloalkyl group such as an nyl group or an adamantyl group is preferable. Among them, alicyclic groups having a bulky structure having 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are contained in the membrane in the post-exposure heating step. Diffusibility can be suppressed, which is preferable from the viewpoint of 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, or a pyridine ring are preferable.

Further, as the cyclic organic group, a lactone structure can also be mentioned, and as a specific example, a lactone structure represented by the following general formulas (LC1-1) to (LC1-17) can be mentioned.

The cyclic organic group may have a substituent, and the substituent may be an alkyl group (which may be linear, branched or cyclic, preferably having 1 to 12 carbon atoms) or cyclo. Alkyl group (which may be monocyclic, polycyclic or spiro ring, preferably 3 to 20 carbon atoms), aryl group (preferably 6 to 14 carbon atoms), hydroxy group, alkoxy group, ester group, amide. Examples thereof include a group, a urethane group, a ureido group, a thioether group, a sulfonamide group, a sulfonic acid ester group and the like. The carbon constituting the cyclic organic group (carbon that contributes to ring formation) may be a carbonyl carbon.
The above-mentioned substituent corresponds to _{Rb 2} in the above-mentioned (LC1-1) to (LC1-17). Further, in the above (LC1-1) to (LC1-17), n2 represents an integer of 0 to 4. When n2 is 2 or more, Rb ₂ existing in plural numbers may be the same or different or may be bonded to form a ring Rb ₂ between the plurality of.

In the general formula (ZI), _{examples of the organic group of R 201} , R ₂₀₂ and R ₂₀₃ include an aryl group, an alkyl group, a cycloalkyl group and the like.
Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , at least one is preferably an aryl group, and 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 also be used. As _{the alkyl group and cycloalkyl group of R 201 to} R ₂₀₃ , preferably, a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms can be mentioned. More preferably, the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and the like. More preferably, the cycloalkyl group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and the like. These groups may further have a substituent. Examples of the substituent include a halogen atom such as a nitro group and a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), and a cycloalkyl group (preferably having 3 to 15 carbon atoms). ), Aryl group (preferably 6 to 14 carbon atoms), alkoxycarbonyl group (preferably 2 to 7 carbon atoms), acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 12 carbon atoms). 7) and the like, but are not limited to these.

Next, the general formulas (ZII) and (ZIII) will be described.
In the general formulas (ZII) and (ZIII), R _{204 to} R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.
The aryl group of 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 and the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, benzothiophene and the like.
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, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group), a carbon. The number 3 to 10 cycloalkyl groups (cyclopentyl group, cyclohexyl group, norbornyl group) can be mentioned.

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 an alkyl group (for example, 1 to 15 carbon atoms) and a cycloalkyl group (for example, 3 to 15 carbon atoms). ), An aryl group (for example, 6 to 15 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, a phenylthio group and the like.

Further, in the 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.

Hereinafter, specific examples of the general formulas (ZI) to (ZIII) will be shown, but the present invention is not limited thereto.

^{In the present invention, the photoacid generator has a volume of 130 Å 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. It may be a compound that generates an acid having a size of (more preferably sulfonic acid), and more preferably a compound that generates an acid (more preferably sulfonic acid) having a volume of 190 Å ³ or more. It is more preferably a compound that generates an acid having a size of 270 Å ³ or more (more preferably sulfonic acid), and a compound that generates an acid having a volume of 400 Å ³ or more (more preferably sulfonic acid). Especially preferable. However, from the viewpoint of sensitivity and coating solvent solubility, the volume is more preferably preferably 2000 Å ³ or less, is 1500 Å ³ or less. The above 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, then the most stable conformation of each acid is determined by the molecular force field calculation using the MM3 method with this structure as the initial structure, and then. The "accessible volume" of each acid can be calculated by calculating the molecular orbital of these most stable conformations using the PM3 method.
In the present invention, a photoacid generator that generates the acids exemplified below by irradiation with active light or radiation is preferable. In addition, the calculated value of the volume is added to a part of the example (unit: Å ³ ). The calculated value obtained here is the volume value of the acid in which the proton is bonded to the anion portion.

Examples of the photoacid generator include paragraphs <0368> to <0377> of Japanese Patent Application Laid-Open No. 2014-41328 and paragraphs <0240> to <0262> of Japanese Patent Application Laid-Open No. 2013-228681 (corresponding US Patent Application Publication No. 2015/004533). <0339>) of the specification can be incorporated, and these contents are incorporated in the present specification. In addition, the following compounds can be mentioned as preferable specific examples, but the present invention is not limited thereto.

The photoacid generator may be used alone or in combination of two or more.
The content of the photoacid generator in the actinic light-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 8 to 40% by mass. In particular, in order to achieve both high sensitivity and high resolution when exposed to an electron beam or extreme ultraviolet rays, the content of the photoacid generator is preferably high, more preferably 10 to 40% by mass, and most preferably 10 to 10. It is 35% by mass.

(C) Solvent A solvent can be used when preparing a sensitive light-sensitive or radiation-sensitive resin composition by dissolving each of the above-mentioned components. Examples of the solvent that can be used include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactate alkyl ester, alkyl alkoxypropionate, cyclic lactone having 4 to 10 carbon atoms, and a ring having 4 to 10 carbon atoms. Examples thereof 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, and propylene glycol monoethyl. Preferable 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.

As the lactate alkyl ester, for example, methyl lactate, ethyl lactate, propyl lactate and butyl lactate are preferably mentioned.
Preferred 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, and γ-. Caprolactone, γ-octanoic lactone and α-hydroxy-γ-butyrolactone are preferred.

Examples of the monoketone compound having 4 to 10 carbon atoms and which may contain a ring include 2-butanone, 3-methylbutanone, pinacol, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone and 4-. Methyl-2-pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,5-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-nonanonone, 3-nonanonone, 5-nonanonone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one, 3-penten-2-one , Cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone , 4-Ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methylcycloheptanone are preferable. ..

As the alkylene carbonate, for example, propylene carbonate, vinylene carbonate, ethylene carbonate and butylene carbonate are preferably mentioned.
Alkoxy alkyl acetates include, for example, -2-methoxyethyl acetate, -2-ethoxyethyl acetate, -2- (2-ethoxyethoxy) ethyl acetate, -3-methoxy-3-methylbutyl acetate, -1-methoxy-acetate. 2-propyl is preferably mentioned.
Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.
Examples of the solvent that can be preferably used include a solvent having a boiling point of 130 ° C. or higher at normal temperature and pressure. 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, acetate Examples thereof include -2- (2-ethoxyethoxy) ethyl and propylene carbonate.
In the present invention, the above-mentioned solvent may be used alone, or two or more kinds may be used in combination.

In the present invention, a mixed solvent in which a solvent containing a hydroxyl group in the structure and a solvent not containing a hydroxyl group are mixed may be used as the 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. Propylene glycol monomethyl ether and ethyl lactate are particularly preferable.
Examples of the hydroxyl group-free solvent include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, and dimethyl sulfoxide. Among these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, and butyl acetate are particularly preferable, and propylene glycol monomethyl ether acetate and ethyl ethoxypropionate are particularly preferable. , 2-Heptanone is most preferred.
The mixing ratio (mass) of the hydroxyl group-containing solvent and the hydroxyl group-free solvent is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, and further preferably 20/80 to 60/. 40. A mixed solvent containing 50% by mass or more of a solvent containing no hydroxyl group is particularly preferable in terms of coating uniformity.

The solvent is preferably a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.

As the solvent, for example, the solvent described in paragraphs 0013 to 0029 of JP-A-2014-219664 can also be used.

(E) Basic Compound The actinic light-sensitive or radiation-sensitive resin composition preferably contains the (E) basic compound in order to reduce the change in performance with time from exposure to heating.
As the basic compound, preferably, a compound having a structure represented by the following formulas (A1) to (E1) can be mentioned.

In the general formulas (A1) and (E1), ^R200 , ^R201 and ^R202 may be the same or different, and may be the same or different, and may be a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms), or a cycloalkyl group (preferably carbon). It represents a number 3 to 20) or an aryl group (preferably 6 to 20 carbon atoms), where R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring.

Regarding the above alkyl group, as the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferable.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and represent an alkyl group having 1 to 20 carbon atoms.
It is more preferable that the alkyl groups in these general formulas (A1) and (E1) are unsubstituted.

Preferred compounds include guanidine, aminopyrrolidin, pyrazole, pyrazoline, piperazine, aminomorpholin, aminoalkylmorpholin, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure and onium carboxylate. Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole and the like. Compounds having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] nona-5-ene, 1,8-diazabicyclo [5,4,0]. ] Undeca-7-en and the like can be mentioned. Compounds having an onium hydroxide structure include triarylsulfonium hydroxides, phenacylsulfonium hydroxides, sulfonium hydroxides having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxides and tris (t-butylphenyl) sulfoniums. Hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide and the like can be mentioned. Examples of the compound having an onium carboxylate structure include those in which the anion portion of the compound having an onium hydroxide structure is carboxylated, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkyl carboxylate. 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, tris (methoxyethoxyethyl) amine and the like. Examples of the aniline derivative having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline and the like.

Preferred basic compounds 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. The amine compound has a cycloalkyl group (preferably 3 to 20 carbon atoms) or an aryl group (preferably 3 to 20 carbon atoms) in addition to the alkyl group as long as at least one alkyl group (preferably 1 to 20 carbon atoms) is bonded to the nitrogen atom. Preferably, 6 to 12) carbon atoms may be bonded to the nitrogen atom.
Further, it is preferable that the amine compound has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more, preferably 3 to 9, and 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 It is an 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. The ammonium salt compound has a cycloalkyl group (preferably 3 to 20 carbon atoms) or an aryl group in addition to the alkyl group as long as at least one alkyl group (preferably 1 to 20 carbon atoms) is bonded to the nitrogen atom. (Preferably 6 to 12 carbon atoms) may be bonded to the 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 one or more, preferably 3 to 9, and 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 It is an ethylene group.
Examples of the anion of the ammonium salt compound include a halogen atom, a sulfonate, a borate, a phosphate and the like, and among them, a halogen atom and a sulfonate are preferable. Chloride, bromide, and iodide are particularly preferable as the halogen atom, and organic sulfonate having 1 to 20 carbon atoms is particularly preferable as the sulfonate. 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 group, acyl group, aryl group and the like. Specific examples of the alkyl sulphonate include methane sulphonate, ethane sulphonate, butane sulphonate, hexane sulphonate, octane sulphonate, benzyl sulphonate, trifluoromethane sulphonate, pentafluoroethane sulphonate, and nonafluorobutane sulphonate. 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 and cyclohexyl. Examples of other substituents include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano, a nitro, an acyl group, an acyloxy group and the like.

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 the 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. And so on. The substituent of the substituent may be any of 2 to 6 positions. The number of substituents may be 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 one or more, preferably 3 to 9, and 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 It is an ethylene group.

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

(A compound (PA) that has a proton-accepting functional group and decomposes by irradiation with active light or radiation to reduce or eliminate the proton-accepting property, or to generate a compound that has changed from proton-accepting property to acidic. )
The composition according to the present invention has a proton-accepting functional group as a basic compound, and is decomposed by irradiation with active light or radiation to reduce, eliminate, or have proton-accepting properties. A compound [hereinafter, also referred to as compound (PA)] that generates a compound that has changed to acidic may be further contained.

A proton-accepting functional group is a functional group having a group or an electron that can electrostatically interact with a proton, 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 shown in the following general formula.

Preferred partial structures of the proton acceptor functional group include, for example, crown ethers, azacrown ethers, 1-3-order amines, pyridines, imidazoles, pyrazine structures and the like.

The compound (PA) is decomposed by irradiation with active light or radiation to generate a compound whose proton acceptor property is reduced or eliminated, or whose proton acceptor property is changed to acidic. Here, the decrease or disappearance of the proton acceptor property, or the change from the proton acceptor property to the acidity is a change in the proton acceptor property due to the addition of a proton to the proton acceptor property functional group. This means that when a proton adduct is formed from a compound (PA) having a proton-accepting functional group and a proton, the equilibrium constant in its chemical equilibrium decreases.

Specific examples of the compound (PA) include the following compounds. Further, as a specific example of the compound (PA), for example, those described in paragraphs 0421 to 0428 of JP-A-2014-413328 and paragraphs 0108 to 0116 of JP-A-2014-134686 can be incorporated. , These contents are incorporated herein by reference.

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

The amount of the basic compound used is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content of the actinic cheilitis or radiation-sensitive composition.

The ratio of the photoacid generator and the basic compound used in the composition is preferably photoacid generator / basic compound (molar ratio) = 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and preferably 300 or less from the viewpoint of suppressing a decrease in resolution due to the thickening of the resist pattern over time from exposure to heat treatment. The photoacid generator / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

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

(A') Hydrophobic Resin The actinic light-sensitive or radiation-sensitive resin composition may have a hydrophobic resin (A') in addition to the resin (A).
Hydrophobic resins are preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, they do not necessarily have to have hydrophilic groups in the molecule and polar / non-polar substances are uniformly mixed. It does not have to contribute to.
The effects 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.

Hydrophobic resin from the viewpoint of uneven distribution in the film surface layer, "fluorine atom", "silicon atom", and has any one or more "CH ₃ partial structure contained in the side chain portion of the resin" It is preferable, and it is more preferable to have two or more kinds. Further, the hydrophobic resin preferably contains a hydrocarbon group having 5 or more carbon atoms. These groups may be contained in the main chain of the resin or may be substituted in the side chain.

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

When the hydrophobic resin contains a fluorine atom, the partial structure having a fluorine atom 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. preferable.
The alkyl group having a fluorine atom (preferably 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 the 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 and a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than the fluorine atom. ..
Examples of repeating units having a fluorine atom or a silicon atom include those exemplified in paragraph 0519 of US2012 / 0251948A1.

Further, as described above, the hydrophobic resin may also preferably comprise a CH ₃ partial structure side chain moiety.
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, the methyl group directly bonded to the main chain of the hydrophobic resin (for example, the α-methyl group of the repeating unit having a methacrylic acid structure) contributes to the uneven distribution of the surface of the hydrophobic resin due to the influence of the main chain. small order, and it shall not be included in the CH ₃ partial structures in the present invention.

Regarding the hydrophobic resin, the descriptions of <0348> to <0415> of JP-A-2014-010245 can be referred to, and these contents are incorporated in the present specification.

As the hydrophobic resin, those described in JP-A-2011-24801, JP-A-2010-175859, and JP-A-2012-032544 can also be preferably used.

(F) Surfactant The actinic light-sensitive or radiation-sensitive resin composition may further contain a surfactant (F). By containing a surfactant, it is possible to form a pattern having less adhesion and development defects with good sensitivity and resolution when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less is used. 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 the surfactant described in <0276> of US Patent Application Publication No. 2008/0248425. In addition, Ftop EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafuck F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Co., Ltd.); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troysol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toa Synthetic Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); Gemco Co., Ltd.); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos Co., Ltd.) You may. The polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

Further, as the surfactant, in addition to the known ones as shown above, 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) is used. It may be synthesized. 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-2002-090991.
In addition, surfactants other than the fluorine-based and / or silicon-based surfactants described in <0280> of US Patent Application Publication No. 2008/0248425 may be used.

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

When the actinic light-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. It is ~ 2% by mass, more preferably 0.0005 to 1% by mass.

(G) Other Additives The active light-sensitive or radiation-sensitive resin composition is a dissolution-inhibiting compound, a dye, a plastic agent, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developing solution. (For example, a phenol compound having a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxy group) may be further contained.

The sensitive light-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 and its solubility in an organic developer is reduced.

[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 upper layer of 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 the 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 JP2014-059543A. As the hydrophobic resin, for example, the above-mentioned hydrophobic resin (A') can be used.
When a developer containing an organic solvent is used in the developing step, for example, it is preferable to form an upper layer film containing a basic compound as described in JP2013-61648A on the resist film. .. Specific examples of the basic compound that can be contained in the upper layer film include the basic compound (E).
Further, 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.
Further, the upper layer film may contain a photoacid generator. As the photoacid generator, the same photoacid generator (for example, the photoacid generator (B) described above) that can be contained in the actinic cheilitis or radiation-sensitive composition can be used.
Hereinafter, the resin 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 upper layer film forming composition is not particularly limited, but is a hydrophobic resin that can be contained in the actinic cheilitis or radiation-sensitive composition (for example, the above-mentioned hydrophobic resin (A')). ) Can be used.
Regarding the hydrophobic resin, Japanese Patent Application Laid-Open Nos. 2013-61647 <0017> to <0023> (corresponding US Patent Publication Nos. 2013/24438 <0017> to <0023>) and Japanese Patent Application Laid-Open No. 2014-56194. The description of <0016> to <0165> of the above can be taken into consideration, and these contents 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 efficiency of secondary electron generation and the efficiency of acid generation from a compound that generates acid by active light or radiation are increased, especially during electron beam or EUV exposure, and a pattern is obtained. The effect of high sensitivity and high resolution can be expected at the time of formation.

The weight average molecular weight of the resin is preferably 3,000 to 100,000, more preferably 3,000 to 30,000, and most preferably 5,000 to 20,000. The blending amount of the resin in the composition for forming the upper layer film is preferably 50 to 99.9% by mass, more preferably 60 to 99.7% by mass, still more preferably 70 to 99.5% by mass, based on the total solid content. , 80-99.0% by mass is even more preferable.

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

Further, a composition for forming an upper layer film is composed of at least one resin (XA) having a fluorine atom and / or a silicon atom, and a resin (XB) having a content of fluorine atoms and / or silicon atoms smaller than that of the resin (XA). More preferably. As a result, when the upper layer film is formed, the resin (XA) is unevenly distributed on the surface of the upper layer film, so that the 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, and 0.1 to 1% by mass, based on the total solid content contained in the composition for forming the upper layer film. 8% by mass is more preferable, and 0.1 to 5% by mass is particularly preferable. The content of the resin (XB) is preferably 50 to 99.9% by mass, more preferably 60 to 99.9% by mass, and 70 to 99. 9% by mass is more preferable, and 80 to 99.9% by mass is particularly preferable.

The resin (XB) preferably has a form in which it does not substantially contain a fluorine atom and a silicon atom. In this case, specifically, the total content of the repeating unit having a fluorine atom and the repeating unit having a silicon atom is determined. It is preferably 0 to 20 mol%, more preferably 0 to 10 mol%, even more preferably 0 to 5 mol%, particularly preferably 0 to 3 mol%, ideally, relative to all repeating units in the resin (XB). Is 0 mol%, that is, it does not contain fluorine atoms and silicon atoms.

<Method of preparing the composition for forming the upper layer film (top coat composition)>
In the composition for forming an upper layer film, it is preferable that each component is dissolved in a solvent and filtered by a filter. 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, still more preferably 0.03 μm or less. A plurality of types of filters may be connected in series or in parallel. Further, the composition may be filtered a plurality of times, and the step of filtering the composition a plurality of times may be a circulation filtration step. Further, the composition may be degassed before and after the filter filtration. The composition for forming an upper layer film preferably 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, further preferably 1 ppm or less, and particularly preferably not substantially contained (below the detection limit of the measuring device). ..

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

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

The film thickness of the upper layer film is not particularly limited, but is usually formed to have a thickness of 5 nm to 300 nm, preferably 10 nm to 300 nm, more preferably 20 nm to 200 nm, and further preferably 30 nm to 100 nm from the viewpoint of transparency to an exposure light source. ..
After forming the upper layer film, the substrate is heated (PB) as needed.
From the viewpoint of resolvability, the refractive index of the upper layer film is preferably close to the refractive index of the actinic cheilitis or radiation-sensitive film.
The upper film is preferably insoluble in the immersion liquid, and more preferably insoluble in water.
From the viewpoint of immersion liquid followability, the receding contact angle (23 ° C.) of the immersion liquid with respect to the upper layer membrane is preferably 50 to 100 degrees, and is preferably 80 to 100 degrees. More preferred.
In immersion exposure, the immersion liquid needs to move on the wafer in accordance with the movement of the exposure head scanning on the wafer at high speed to form an exposure pattern. The contact angle of the immersion liquid with the light-emitting 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 peeling agent may be used separately. As the release agent, a solvent having a small penetration into the sensitive light-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 at the same time as the development of the sensitive light-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 cheilitis or radiation-sensitive film.

From the viewpoint of peeling with an organic developer, the upper film preferably has a dissolution rate in an organic developer of 1 to 300 nm / sec, more preferably 10 to 100 nm / sec.
Here, the dissolution rate of the upper layer film in an organic developer is the rate of decrease in film thickness when the upper layer film is exposed to the developer after being formed into a film, and in the present invention, it is immersed in butyl acetate at 23 ° C. It is the speed of the time.
By setting the dissolution rate of the upper film in an organic developer to 1 nm / sec or more, preferably 10 nm / sec or more, the effect of reducing the occurrence of development defects after developing the sensitive light-sensitive or radiation-sensitive film can be obtained. is there. Further, by setting the temperature to 300 nm / sec or less, preferably 100 nm / sec, the line edge of the pattern after developing the sensitive light-sensitive or radiation-sensitive film is probably due to the effect of reducing the exposure unevenness during immersion exposure. It has the effect of improving roughness.
The upper film may be removed by using another known developer, for example, an alkaline aqueous solution. Specific examples of the alkaline aqueous 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 organic impurities is applied to a semiconductor device manufacturing process, among the organic impurities, a high boiling point organic impurity having a boiling point of 300 ° C. or higher remains without volatilization, to a remarkable extent. 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 organic impurities having a boiling point of 300 ° C. or higher in the treatment liquid is 0.001 mass ppm to 30 mass ppm with respect to the total mass of the treatment liquid when used in the semiconductor device manufacturing process, the substrate It was confirmed that it is preferable from the viewpoint of suppressing defect defects.

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 treatment liquid, for example, when the treatment liquid is used as a developing solution and brought into contact with a substrate. It is preferable from the viewpoint of suppressing that organic impurities do not volatilize and remain on the surface of the substrate, resulting in defective defects.
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 treatment liquid, for example, when the treatment liquid is used as a developing solution and brought into contact with a substrate, it is baked. It is more preferable from the viewpoint of suppressing the cause of defects (development failure) in order to prevent organic impurities having a boiling point of 300 ° C. or higher from remaining on the substrate even after the step.
Organic impurities having a boiling point of 300 ° C. or higher in the treatment liquid include components such as diisononyl phthalate (DOP, boiling point 385 ° C.) eluted from the O-ring, diisononyl phthalate (DINP, boiling point 403 ° C.), and 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.

The content of organic impurities having a boiling point of 300 ° C. or higher in the treatment liquid is measured by DI-MS (Direct Injection Mass Chromatography).
Examples of the method for keeping the content of organic impurities having a boiling point of 300 ° C. or higher in the treatment liquid within the above range include the methods mentioned in the purification step described later.

<Metal component (metal impurity) containing an element selected from the group consisting of Fe, Cr, Ni and Pb>
In the present invention, the treatment liquid also contains at least one element selected from the group consisting of Fe, Cr, Ni and Pb, and the content of each element is 0.001 to 1 with respect to the total mass of the treatment liquid. It is preferably 100 mass ppt, more preferably 0.001 to 50 mass ppt, and further preferably 0.001 to 10 mass ppt from the viewpoint of defect suppression. Here, the content of each element in the treatment liquid indicates the content of each element selected from the group consisting of Fe, Cr, Ni and Pb in the treatment liquid.
The metal component is present in the organic solvent to a certain extent, and may be mixed in the treatment liquid 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 particularly large effect on defect performance.
If the content of the metal component containing at least one 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 1 mass When it is ppt or less, a more remarkable effect is obtained due to the more remarkable defect suppressing ability.
When the content of the metal component containing at least one element selected from the group consisting of Fe, Cr, Ni and Pb exceeds 100 mass ppt with respect to the total mass of the treatment liquid, metal particles (deterioration of defects). ), And if it exceeds 0.001 mass ppt, the production control can be performed stably, and the quality of each production lot becomes stable.
When a plurality of metal components containing an element selected from the group consisting of Fe, Cr, Ni and Pb are contained, the total amount thereof preferably satisfies the above range.
The content of metal impurities in the treatment liquid is measured by ICP-MS (inductively coupled plasma mass spectrometer). If the measurement is less than 1 mass ppt, it is difficult to measure with the undiluted solution. Therefore, the treatment solution was concentrated as necessary to perform the measurement.
Examples of the method for keeping the content of metal impurities in the treatment liquid within 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 adsorption member).
In the present invention, the treatment liquid also contains at least one element selected from the group consisting of Fe, Cr, Ni and Pb, and the total amount of the elements is 0.001 to 100 mass ppt with respect to the total mass of the treatment liquid. Is preferable. From the viewpoint of defect suppression, the total content of at least one element selected from the group consisting of Fe, Cr, Ni and Pb in the treatment liquid is 100 mass ppt or less with respect to the total mass of the treatment liquid. More preferred from. It is preferable that the treatment liquid contains at least one element selected from the group consisting of Fe, Cr, Ni and Pb, and the total amount of the elements is 0.001 to 50 mass ppt with respect to the total mass of the treatment liquid. It is more preferably 0.001 to 10 mass ppt, and further preferably 1 mass ppt or less from the viewpoint of defect suppression.

(substrate)
The "base" as used in the present invention includes, for example, a semiconductor substrate made of a single layer and a semiconductor substrate made of multiple layers.
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, or GaAs, or any combination thereof.
In the case of a semiconductor substrate composed of multiple layers, the configuration is not particularly limited, and for example, exposed integration of interconnect features such as metal wires and dielectric materials on the above-mentioned semiconductor substrate such as silicon. It may have a circuit structure. Metals and alloys used in interconnect structures include, but are limited to, aluminum and copper and alloyed aluminum, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten. It is not something that is done. Further, a layer such as an interlayer dielectric layer, silicon oxide, silicon nitride, silicon carbide and carbon-doped silicon oxide may be provided on the semiconductor substrate.

<Manufacturing method of treatment liquid>
The treatment liquid of the present invention preferably undergoes the following purification steps in order to keep the contents of metal components, organic impurities having a boiling point of 300 ° C. or higher, and water within a desired range.

(Refining process)
The purification step may be carried out 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 the raw material used for producing the 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. for forming the treatment liquid.
Further, the purification treatment II is a treatment for purifying the organic solvent having a boiling point of less than 300 ° C., which constitutes the treatment liquid, during and / or after the production.
Further, the purification treatment III is a treatment in which each component is purified before mixing two or more kinds of organic solvents having a boiling point of less than 300 ° C. at the time of producing the treatment liquid.
Further, the purification treatment IV is a treatment in which two or more kinds of organic solvents having a boiling point of less than 300 ° C. are mixed at the time of producing the treatment liquid, and then the mixture is purified.
As described above, purification is preferable to obtain the desired treatment liquid. Purification may be carried out after purifying each organic solvent and then mixing, or after mixing each organic solvent, purification may be performed. In particular, a method of blending a purified organic solvent is preferable in that the blend ratio of the organic solvent can be produced to be constant.
Each of the purification treatments I to IV may be carried out only once or twice or more.
In addition, as the organic solvent to be used, high-purity grade products (particularly those having a low content of the above-mentioned organic impurities, metal impurities, water, etc.) are purchased, and further, the purification treatment described later is performed on them. Can be used.

An example of the purification process is shown below. In the following description, the purification target in the purification step is simply collectively referred to as "the liquid to be purified".
As an example of the purification process, a first ion exchange treatment for performing an ion exchange treatment of the liquid to be purified, a dehydration treatment for dehydrating the liquid to be purified after the first ion exchange treatment, and a distillation for distilling the liquid to be purified after the dehydration treatment. An embodiment 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 carried out in this order. Can be mentioned. In the following, the above purification step 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 treatment for dehydrating the liquid to be purified is performed, a distillation treatment for distilling the liquid to be purified after the dehydration treatment, a first ion exchange treatment for ion exchange treatment of the liquid to be purified, and a second ion. The organic impurity removing treatment for removing the organic impurities in the liquid to be purified after the exchange treatment may be carried out in this order.

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

According to the dehydration treatment, water in the liquid to be purified can be removed. Further, when zeolite described later (particularly, molecular sieve (trade name) manufactured by Union Showa Co., Ltd.) is used in the dehydration treatment, olefins can also be removed.
Examples of the dehydrating means used for the dehydration treatment include a dehydration film, a water adsorbent insoluble in the liquid to be purified, an aeration replacement device using a dry inert gas, and a heating or vacuum heating device.
When a dehydrated membrane is used, membrane dehydration is performed by osmotic vaporization (PV) or vapor permeation (VP). The dehydrated membrane is configured as, for example, a permeable membrane module. As the dehydration membrane, a membrane made of a polymer-based material such as polyimide-based, cellulosic-based and polyvinyl alcohol-based, or an inorganic-based material such as zeolite can be used.
The water adsorbent is used by adding it to the liquid to be purified. Examples of the water adsorbent include zeolite, diphosphorus pentoxide, silica gel, calcium chloride, sodium sulfate, magnesium sulfate, anhydrous zinc chloride, fuming sulfuric acid, soda lime and the like.

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 fine particles if the metal components are fine particles), and a subject. Water in the purified liquid can be removed.
The distillation means is composed of, for example, a single-stage distillation apparatus. Impurities are concentrated in a distillation apparatus or the like by the distillation treatment, but in order to prevent a part of the concentrated impurities from flowing out, a part of the liquid in which the impurities are concentrated is periodically used in the distillation means. Alternatively, it is preferable to provide means for constantly discharging to the outside.

According to the second ion exchange treatment, when impurities accumulated in the distillation apparatus flow out, they can be removed, and eluates from pipes such as stainless steel (SUS) used as a liquid feeding line can be removed.
Examples of the second ion exchange means include those in which an ion exchange resin is filled in a tower-shaped container and an ion adsorption film, and an ion adsorption film is preferable because it can be processed at a high flow velocity. Examples of the ion adsorption membrane include Neocepta (trade name, manufactured by Astom Co., Ltd.).

Each of the above-mentioned treatments is preferably carried out in a hermetically sealed state and in an inert gas atmosphere in which water is unlikely to be mixed into the liquid to be purified.
Further, 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 water as much as possible. This is because in an inert gas atmosphere of −70 ° C. or lower, the water concentration in the gas phase is 2 mass ppm or less, so that the possibility of water being mixed in the solution (the liquid to be purified) is low.

Examples of the purification step include, in addition to the above treatment, an adsorption purification treatment of a metal component using silicon carbide, which is described in International Publication No. WO2012 / 043496.

According to the organic impurity removing treatment, high boiling point 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 can be removed.
As the organic impurity removing means, for example, it can be carried out by an organic impurity adsorbing member provided with an organic impurity adsorbing filter capable of adsorbing organic impurities. The organic impurity adsorption member is usually configured to include the organic impurity adsorption filter and a base material for fixing the impurity adsorption filter.
The organic impurity adsorption filter has an organic substance skeleton capable of interacting with organic impurities on the surface from the viewpoint of improving the adsorption performance of organic impurities (in other words, the surface is modified by the organic substance skeleton capable of interacting with organic impurities. It is preferable. It should be noted that having an organic skeleton capable of interacting with organic impurities on the surface means that the surface of the base material constituting the organic impurity adsorption filter described later is provided with the organic skeleton capable of interacting with the organic impurities. Take as an example.
Examples of the organic substance skeleton capable of interacting with organic impurities include a chemical structure capable of reacting with organic impurities and capturing the organic impurities in an organic impurity adsorption filter. More specifically, when the organic impurity contains dioctyl phthalate, diisononyl phthalate, dioctyl adipate, or dibutyl phthalate, the organic skeleton includes a benzene ring skeleton. When ethylene propylene rubber is contained as the organic impurity, the organic skeleton includes an alkylene skeleton. When n-long-chain alkyl alcohol (structural isomer when 1-long-chain alkyl alcohol is used as the solvent) is contained as the 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, and fluororesin supporting activated carbon.
Further, as the organic impurity removing filter, a filter in which activated carbon described in JP-A-2002-273123 and JP-A-2013-150979 is fixed to a non-woven fabric can also be used.

Further, the organic impurity removing treatment is not limited to the mode using the organic impurity adsorption filter capable of adsorbing the organic impurities as described above, and may be, for example, a mode of physically supplementing the organic impurities. 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 therefore can be physically supplemented by using a filter having a pore size of about 1 nm. Is.
For example, when dioctyl phthalate is contained as an organic impurity, the structure of dioctyl phthalate is larger than 10 Å (= 1 nm). Therefore, by using an organic impurity removing filter having a pore diameter of 1 nm, dioctyl phthalate cannot pass through the pores of the filter. That is, dioctyl phthalate is physically trapped by the filter and is therefore removed from the liquid to be purified. As described above, the removal of organic impurities can be achieved 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 “filter member” described later, and a filter having a pore diameter of less than 3 nm is used as an “organic impurity removing filter”.
In the present specification, 1 Å (angstrom) corresponds to 0.1 nm.

Further, the purification step of the present invention may further include, for example, purification treatment V and purification treatment VI described later. The purification treatment V and the purification treatment VI may be carried out at any timing, and examples thereof include after the purification step IV is carried out.
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 treatment V and the purification treatment VI will be described.

In the purification treatment VI, as an example of the means for removing metal ions, filtering using a metal ion adsorption member provided with a metal ion adsorption filter can be mentioned 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 according to a target purification level. The metal ion adsorption member is usually configured to include the metal ion adsorption filter and a base material for fixing the metal ion adsorption filter.
The metal ion adsorption filter has a function of adsorbing metal ions in the liquid to be purified. Further, the metal ion adsorption filter is preferably a filter capable of ion exchange.
Here, the metal ion to be adsorbed is not particularly limited, but Fe, Cr, Ni and Pb are preferable from the viewpoint of easily causing defects in the semiconductor device.
The metal ion adsorption filter preferably has an acid group on its 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 base material (material) constituting the metal ion adsorption filter include cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, and fluororesin.

An example of the purification treatment VI is an embodiment in which the filtration means is carried out by using a filtration member provided with a filter having a particle size removal diameter of 20 nm or less. By adding the above filter, the liquid to be purified can remove particulate impurities from the liquid to be purified. Here, the "particulate impurities" include particles such as dust, dust, organic solids and inorganic solids contained as impurities in the raw materials used in the production of the liquid to be purified, and during the purification of the liquid to be purified. Examples include dust, dust, particles of organic solids and inorganic solids brought in as contaminants, and those that finally exist as particles without being dissolved in the liquid to be purified are applicable.
The "particulate impurities" also include colloidal impurities containing metal atoms. The metal atom is not particularly limited, but is derived 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 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. Impures tend to colloid. With the metal ion adsorption member, it tends to be difficult to remove colloidal impurities. Therefore, by using a filter having a particle size removal diameter of 20 nm or less (for example, a microfiltration membrane having a pore diameter of 20 nm or less), colloidal impurities can be effectively removed.
The particulate impurities have a size that can be removed by a filter having a particle size removal diameter of 20 nm or less, and specifically, particles having a diameter of 20 nm or more. In the present specification, particulate impurities may be referred to as "coarse particles".
Among them, the particle removal diameter of the filter is preferably 1 to 15 nm, more preferably 1 to 12 nm. When the particle size is 15 nm or less, finer particulate impurities can be removed, and when the particle size is 1 nm or more, the filtration efficiency of the liquid to be purified is improved.
Here, the particle size removal means the minimum size of particles that can be removed by the filter. For example, when the removal particle 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, fluororesin and the like.

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

The liquid to be purified obtained by obtaining each of these treatments can be used in the composition of the treatment liquid of the present invention or as the treatment liquid of the present invention itself.
As an example of the above-mentioned purification step, the case where all the treatments are performed is shown, but the present invention is not limited to this, and each of the above treatments may be performed alone or in combination of a plurality of the above treatments. .. Further, each of the above processes may be performed once or a plurality of times.

In addition to the above purification step, as a method for keeping the content of organic impurities, metal components and water having a boiling point of 300 ° C. or higher contained in the treatment solution within a desired range, the boiling point of the treatment solution is less than 300 ° C. It is also possible to store the raw material of the organic solvent or the solution itself in a container in which impurities are less likely to elute. Further, there is also a method of lining the inner wall of the pipe with a fluororesin so that the metal component does not elute from the “pipe” or the like during the production of the treatment liquid.

[Container (container)]
The treatment liquid of the present invention can be filled in an arbitrary container, stored, transported, and used as long as corrosiveness does not become a problem.
As the container, it is preferable that the container has a high degree of cleanliness and less elution of impurities for semiconductor applications.
Specific examples of the containers that can be used include, but are not limited to, the "clean bottle" series manufactured by Aicello Chemical Corporation and the "pure bottle" manufactured by Kodama Resin Industry. The inner wall of the container (the wetted portion in contact with the solution in the container) is preferably formed of a non-metallic material.
Non-metallic materials include polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, ethylene tetrafluoride resin (PTFE), ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer (PFA), ethylene tetrafluoride-hexfluoride. Propropylene copolymer resin (FEP), ethylene tetrafluoride-ethylene copolymer resin (ETFE), ethylene trifluoride-ethylene copolymer resin (ECTFE), vinylidene fluoride resin (PVDF), ethylene trifluoride copolymer At least one selected from the group consisting of resin (PCTFE) and vinyl fluoride resin (PVF) is more preferable.
In particular, among the above, when a container having an inner wall made of a fluororesin is used, it is said that ethylene or propylene oligomer is eluted as compared with a case where a container having an inner wall made of polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin is used. The occurrence of defects can be suppressed.
Specific examples of such a container whose inner wall is a fluororesin include a FluoroPure PFA composite drum manufactured by Entegris. In addition, it is described on pages 4 of the special table No. 3-502677, page 3 of the pamphlet of International Publication No. 2004/016526, and pages 9 and 16 of the pamphlet of International Publication No. 99/46309. Containers can also be used.
When the inner wall of the non-metal material is used, it is preferable that the elution of the organic component in the non-metal material into the treatment liquid is suppressed.

Further, in addition to the above-mentioned non-metal material, quartz or a metal material (more preferably, an electropolished metal material, in other words, an electropolished metal material) is also preferably used for the inner wall of the container.
The metal material (particularly, the metal material used for producing the 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, and examples thereof include 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. Among them, an alloy containing 8% by mass or more of nickel is preferable, and an austenitic stainless steel containing 8% by mass or more of nickel is more preferable. Examples of austenitic stainless steels include SUS (Steel Use Stainless) 304 (Ni content 8% by mass, Cr content 18% by mass), SUS304L (Ni content 9% by mass, Cr content 18% by mass), and SUS316 ( Ni content 10% by mass, Cr content 16% by mass), SUS316L (Ni content 12% by mass, Cr content 16% by mass) and the like.

The method for electrolytically polishing a metal material is not particularly limited, and a known method can be used. For example, the methods described in paragraphs <0011>-<0014> of JP2015-227501 and paragraphs <0036>-<0042> of JP2008-264929 can be used.

It is presumed that the content of chromium in the passivation layer on the surface of the metal material is higher than the content of chromium in the parent phase by electropolishing. Therefore, it is presumed that a solution having a reduced metal component (metal impurities) can be obtained because the metal component does not easily flow out into the solution from the inner wall coated with the electropolished metal material.
The metal material is preferably buffed. The method of buffing is not particularly limited, and a known method can be used. The size of the abrasive grains used for finishing the buffing is not particularly limited, but # 400 or less is preferable because 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 a plurality of stages of buffing, acid cleaning, magnetic fluid polishing, etc., which are performed by changing the count such as the size of the abrasive grains. ..

In the present invention, a container having the container and the treatment liquid contained in the container may be referred to as a solution container.

It is preferable that the inside of these containers is cleaned before filling with the treatment liquid. When the liquid used for cleaning is the treatment liquid of the present invention itself, a diluted solution of the present invention, or an organic solvent contained in the treatment liquid of the present invention, the effect of the present invention can be remarkably obtained. The treatment liquid of the present invention may be bottling, transported and stored in a container such as a gallon bottle or a coated bottle after production. The gallon bottle may or may not be made of glass material.

For the purpose of preventing changes in the components in the treatment liquid during storage, the inside of the container may be replaced with an inert gas (chisso, argon, etc.) having a purity of 99.99995% by volume or more. In particular, a gas having a low water content is preferable. Further, during transportation and storage, the temperature may be at room temperature, but in order to prevent deterioration, the temperature may be controlled in the range of −20 ° C. to 20 ° C.

(Clean room)
It is preferable that the production of the treatment liquid of the present invention, the opening and / or cleaning of the storage container, the handling including the filling of the treatment liquid, the treatment analysis, and the measurement are all performed in a clean room. The clean room preferably meets the 14644-1 clean room standard. It is preferable to satisfy any of ISO (International Organization for Standardization) class 1, ISO class 2, ISO class 3, and ISO class 4, and it is more preferable to satisfy ISO class 1 or ISO class 2, and ISO class 1 is satisfied. Is even more preferable. The handling, treatment analysis, and measurement including the production of the treatment liquid, opening and / or cleaning of the storage container, filling of the treatment liquid, etc. in the examples described later were performed in a class 2 clean room.

(filtering)
The treatment liquid of the present invention, or the organic solvent contained in the treatment liquid, keeps the contents of organic impurities, metal components, and water having a boiling point of 300 ° C. or higher within a desired range, and removes foreign substances, coarse particles, and the like. Therefore, it is preferable that the particles are filtered.
The filter used for filtering can be used without particular limitation as long as it is conventionally used for filtration purposes and the like. Examples of the material constituting the filter include fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, polyethylene, and polyolefin resins such as polypropylene (PP) (high density and ultrahigh molecular weight). ) Etc. can be mentioned. Among these, polyamide resins, PTFE, and polypropylene (including high-density polypropylene) are preferable, and by using a filter formed of these materials, highly polar foreign substances that easily cause particle defects are more effective. In addition to being able to remove the metal components (metal impurities) more efficiently.

The lower limit of the critical surface tension of the filter is preferably 70 mN / m or more. The upper limit is preferably 95 mN / m or less. Above all, the critical surface tension of the filter is more preferably 75 mN / m or more and 85 mN / m or less.
The value of the critical surface tension is the nominal value of the manufacturer. By using a filter having a critical surface tension in the above range, highly polar foreign substances that easily cause particle defects can be removed more effectively, and the amount of metal components (metal impurities) can be reduced more efficiently. ..

The filter used for filtering is not particularly limited as long as it has been conventionally used for filtration purposes and the like. Examples of the material constituting the filter include fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, polyethylene, and polyolefin resins such as polypropylene (PP) (high density and ultrahigh molecular weight). ) Etc. can be mentioned. 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 even more preferably about 0.01 to 0.1 μm. By setting the pore size of the filter within 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 twice or more. When different filters are combined and filtering is performed twice or more, the filters may be of the same type or different types of each other, but they are different types of each other. Is preferable. Typically, it is preferable that the first filter and the second filter differ in at least one of the pore diameter and the constituent material.
It is preferable that the pore diameters of the second and subsequent filters are the same or smaller than the pore diameter of the first filtering. Further, first filters having different pore diameters within the above-mentioned range may be combined. For the hole diameter here, the nominal value of the filter manufacturer can be referred to. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Microfilter Co., Ltd. In addition, "P-nylon filter (pore diameter 0.02 μm, critical surface tension 77 mN / m)" made of polyamide; (manufactured by Nippon Pole Co., Ltd.), "PE clean filter (pore diameter 0.02 μm)" made of high-density polyethylene; (Manufactured by Nippon Pole Co., Ltd.) and "PE clean filter (pore diameter 0.01 μm)" made of high-density polyethylene; (manufactured by Nippon Pole Co., Ltd.) can also be used.

Although not particularly limited, for example, from the viewpoint of being more excellent in the effect of the treatment liquid of the present invention and from the viewpoint of suppressing the increase of particulate metal in the storage of the purified treatment liquid, the solution used in one aspect of the present application is used. The relationship between the filter material used for filtering and the interaction radius (R0) in the Hansen solubility parameter (HSP) space that can be derived from the filter material used for filtering is contained in the treatment solution or the organic solvent contained in the treatment solution. It is a combination that satisfies the relational expression (Ra / R0) ≤ 1 of Ra and R0 when the radius (Ra) of the sphere in the Hansen space that can be derived from the liquid is satisfied, and the process is filtered by the filter material that satisfies these relational expressions. It is preferably an organic solvent contained in the liquid or the treatment liquid. (Ra / R0) ≦ 0.98 is preferable, and (Ra / R0) ≦ 0.95 is more preferable. The lower limit is preferably 0.5 or more, more preferably 0.6 or more, and further preferably 0.7. The mechanism is not clear, but within this range, the formation of particulate metal or the growth of particulate metal during long-term storage is suppressed.
The combination of these filters and the treatment liquid or the organic solvent contained in the treatment liquid is not particularly limited, and examples thereof include those of US Pat. No. 6,2016,089622.

As the second filter, a filter made of the same material as the first filter described above can be used. A filter having the same pore size as the first filter described 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 pore diameter of the second filter to the pore diameter of the first filter (the pore diameter of the second filter / the pore diameter of the first filter). ) Is preferably 0.01 to 0.99, more preferably 0.1 to 0.9, and even more preferably 0.2 to 0.9. By setting the pore size of the second filter within the above range, fine foreign substances mixed in the solution can be removed more reliably.

Further, in the present invention, it is composed of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Pd, and Zn with respect to the treatment liquid or the organic solvent contained in the treatment liquid. When the content of one or more metal elements selected from the group is particularly low (for example, the content of the above-mentioned metal elements is 1000 mass by mass with respect to the treatment liquid or the organic solvent contained in the treatment liquid. Impurities containing these metal elements tend to colloid easily (in the case of ppt or less). Therefore, it tends to be difficult to remove colloidal impurities with the ion adsorption membrane. Therefore, the present inventors have found that colloidal impurity components can be removed by purification using a microfiltration membrane having a pore size of 20 nm or less.

In addition, when 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 precision filtration membrane for removing fine particles having a pore size of 50 nm or more before filtering using a precision filtration membrane having a pore size of 20 nm or less.

The treatment liquid of the present invention or the organic solvent contained in the treatment liquid is preferably purified by using an ion adsorption means in addition to the above-mentioned filter. In the ion adsorption means, the surface of cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, fluororesin 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 preferably an ion adsorption means. The ion adsorbing means modified with an anionic group can remove cations such as Na ion and Ca ion, and the ion adsorbing means modified with a cationic group can remove anions such as Cl ions and acid components. Can be removed. The ion adsorption means may use an anionic group, a cationic group, or a combination thereof, depending on the intended purpose. The ion adsorption means may be a filter.

The above filtration step may be repeated a plurality of times depending on the purpose.

Further, the filter used is preferably treated before filtering the treatment liquid or the organic solvent contained in the treatment liquid. The liquid used for this treatment is not particularly limited, but the solution of the present invention itself, a diluted solution of the present invention, or an organic solvent contained in the treatment liquid of the present invention has the desired effect of the present invention. Is remarkably obtained.

When filtering, the upper limit of the temperature at the time of filtering is preferably room temperature (25 ° C.) or lower, more preferably 23 ° C. or lower, and even more preferably 20 ° C. or lower. The lower limit of the temperature at the time of filtering is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, and even more preferably 10 ° C. or higher.
Filtering can remove particulate foreign matter or impurities, but when performed at the above temperature, the amount of particulate foreign matter or impurities dissolved in the treatment liquid or the organic solvent contained in the treatment liquid is reduced. , Filtering is done more efficiently.

In particular, from the viewpoint of adjusting the content of metal components (metal impurities), it is preferable to filter at the above temperature. Although the mechanism is not clear, it is considered that most of the metal components (metal impurities) exist in a particulate colloidal state. When filtering at the above temperature, some of the metal components (metal impurities) floating in a colloid are aggregated, and these agglomerated substances are efficiently removed by filtering, so that the metal components (metals) are efficiently removed. It is considered that it becomes easy to adjust the content of (impurities) to a predetermined amount.

Since the filtration pressure affects the filtration accuracy, it is preferable that the pressure pulsation during filtration is 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 from the viewpoint of being more excellent in the effect of the present invention, 1.0 L / min / m ² or more is preferable, and 0 .75L / min / ^{m 2} or more preferably, 0.6 L / min / ^{m 2} or more is more preferable.
A differential pressure resistance that guarantees filter performance (the filter does not break) is set in the filter, and when this value is large, the filtration rate can be increased by increasing the filtration pressure. That is, 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, and 0.003 MPa or more and 0. 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 matter or impurities dissolved in the solution can be efficiently reduced by increasing the filtration pressure. When a filter having a pore size smaller than 20 nm is used, it is particularly preferable that the filtration pressure is 0.005 MPa or more and 0.3 MPa or less.

Further, as the pore size of the filtration filter membrane becomes smaller, 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. As it is lowered, this makes it possible to compensate for the decrease in filtration rate.

[Static elimination process]
In the preparation and purification of the treatment liquid of the present invention or the organic solvent contained in the treatment liquid, a static elimination step may be further provided. The static elimination step is a step of reducing the charging potential of a purified product or the like by removing static electricity from at least one selected from the group consisting of a raw material, a reactant, and a purified product (hereinafter referred to as "refined product or the like"). ..
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 in which the purified liquid or the like is brought into contact with the conductive material.
The contact time for bringing the purified liquid or the like into contact with the conductive material is preferably 0.001 to 60 seconds, more preferably 0.001 to 1 second, and even more preferably 0.01 to 0.1 second. Examples of the conductive material include stainless steel, gold, platinum, diamond, glassy carbon and the like.
Examples of the method of bringing the purified liquid or the like into contact with the conductive material include a method of arranging a grounded mesh made of the conductive material inside the conduit and passing the purified liquid or the like through the grounded mesh.

The static elimination step may be performed at any time from the supply of the raw material to the filling of the purified product, and is selected from the group consisting of, for example, the raw material supply step, the reaction step, the liquid preparation step, the purification step, the filtration step, and the filling step. It is preferably contained before at least one step to be carried out. 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. This makes it possible to prevent impurities derived from the container or the like from being mixed into the purified product or the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. Unless otherwise specified, "parts" and "%" are based on mass.
Quantitative analysis of sulfur-containing compounds (for example, JISK2541-6: 2013 "Sulfur content test" with respect to the treatment liquids used in the subsequent development or rinsing (treatment liquids shown in Table 8 and Table 8-No. 2). Method (measured by the method specified in "Method (ultraviolet fluorescence method)") and quantitative analysis of phosphorus compounds (measured as total phosphorus by absorptiometry based on the method specified in JIS K0102: 2013). It was confirmed that the compound was substantially not contained.
Here, "substantially not contained" means that the content (concentration) of these compounds is not detected (less than the detection limit value) when measured by a measurable method.

1. 1. EUV exposure (Examples 1-1 to 1-47, Comparative Examples 1-1 to 1-5)
<Resin (A), etc.>
(Synthesis Example 1) Synthesis of Resin (A-1) 600 g of cyclohexanone was placed in a 2 L flask, and nitrogen was replaced at a flow rate of 100 mL / min for 1 hour. Then, 4.60 g (0.02 mol) of the 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 monomer and 4.60 g (0.02 mol) of the 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 added dropwise to the flask heated to 80 ° C. over 6 hours. After completion of the dropping, the reaction was further carried out at 80 ° C. for 2 hours.
4-acetoxystyrene ・ ・ ・ 48.66 g (0.3 mol)
1-Ethyl cyclopentyl 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 in 3 L of hexane to precipitate the polymer. The filtered solid was dissolved in 500 mL of acetone, added dropwise to 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, and the mixture was heated to 80 ° C. and stirred for 5 hours. The reaction solution was allowed to cool to room temperature and added dropwise to 3 L of distilled water. The filtered solid was dissolved in 200 mL of acetone, dropped again in 3 L of distilled water, and the filtered solid was dried under reduced pressure to obtain a 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 11200, and the molecular weight dispersion (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 monomer used was 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 the dispersity (Mw / Mn) of the resin were calculated by GPC (solvent: THF) measurement. The weight average molecular weight and the degree of dispersion of the other resins shown in the examples were measured by the same method.

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

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

<Photoacid generator (B)>
The following photoacid generators were used.

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

<Solvent (C)>
The following was used as the resist solvent.
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 Table 5 below 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 Table 6 below 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 methylisobutylcarbinol.

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

<EUV exposure evaluation>
Using the resist compositions shown in Table 5, the post-development defect performance and pattern formation performance of the resist were evaluated by the following operations.
[Applying 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 film thickness of 40 nm.
Examples 1-24 are positive resist compositions, and the others are negative resist compositions.

[Applying the composition for forming an upper layer film and baking after coating (PB)]
For Examples 1-30 to 1-37, 1-42 to 1-47, the upper film forming composition (top coat composition) shown in Table 6 above was applied onto the resist film after baking, and then , The PB temperature (unit: ° C.) shown in Tables 9 and 9-2 below was baked for 60 seconds to form an upper film (top coat) having a film thickness of 40 nm.

〔exposure〕
(Evaluation of defect performance after development)
The wafer produced above was subjected to EUV exposure with NA (numerical aperture, Natural Aperture) 0.25 and dipole illumination (Dipole 60x, outer sigma 0.81, inner sigma 0.43). Specifically, the negative type resist is ^{exposed to the entire surface with an exposure amount of 1 mJ / cm 2} without using a mask, and the positive type resist is exposed to a mask with an exposure amount ^{of 200 mJ / cm 2.} The entire surface was exposed without intervention.

(Line with Roughness (LWR) evaluation)
The wafer produced above was subjected to EUV exposure with NA (numerical aperture, Natural Aperture) 0.25 and dipole illumination (Dipole 60x, outer sigma 0.81, inner sigma 0.43). Through a mask containing a pattern (for L / S bridge evaluation) for forming a line-and-space pattern with a pitch of 60 nm and a line width of 40 nm on the wafer, the exposure amount is finished to a line width of 40 nm and a space width of 20 nm. Then, pattern exposure was performed on the entire surface of the wafer.

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

〔developing〕
Then, using a shower-type developing device (ADE3000S manufactured by ACTES Co., Ltd.), the developer (23 ° C.) is spray-discharged at a flow rate of 200 mL / min for 30 seconds while rotating the wafer at 50 rotations (rpm). So, I developed it. As the developing solution, any of the treatment solutions S-1 to S-40 shown in Table 8 and Table 8-No. 2 was used. Table 8 and Table 8-No. 2 show the treatment liquids used in each Example and Comparative Example. The mass ratios in Table 8 and Table 8-No. 2 represent the organic solvents shown in Table 8 and Table 8-No. 2 in order from the left side.

Each treatment liquid was purified as follows.
For the purification of the treatment liquid or the organic solvent contained in the treatment liquid, an apparatus in which a "dehydrating member" was connected to the downstream side of the second metal ion adsorption filter 34 of the organic solvent purification apparatus 100 of FIG. 1 was used.
Here, in the organic solvent refining apparatus 100 of FIG. 1 used in the Example column, a stainless steel wetted portion coated with PTFE was used for the tank 10. Further, as the pump 20, a pump whose wetted portion was coated with PTFE was used. Further, as the supply pipe 60, a tube made of PFA having an outer diameter of 12 mm was used.
Further, for the distillation unit 50, a shelf-type distillation column (10 stages (10 shelves)) made of SUS316 as a material was used.
Further, as the first metal ion adsorption filter 32 and the second metal ion adsorption filter 34, 15 nm IEX PTFE manufactured by Entegris (a filter having a pore size of 15 nm having a sulfo group on the surface of a substrate made of PTFE) was used.
Further, as the filtration member 40, 12 nm PTFE manufactured by Entegris (a filter manufactured by PTFE and having a particle size removal diameter of 12 nm) was used. Further, as the organic impurity adsorbing member 50, a filter in which activated carbon described in JP2013-150979A was fixed to a non-woven fabric was used.
Then, after filling the tank 10 with each of the organic solvents shown in Table 8 and Table 8-No. 2, the object to be purified is circulated once in the direction of the arrow in FIG. 1 and contained in the treatment liquid or the treatment liquid. An organic solvent was obtained.

<Evaluation>
[Measurement of metal components (metal impurities)]
The content of metal atoms contained in the metal impurities in the treatment liquids prepared in each Example and Comparative Example was measured using Agilent 8800 triple quadrupole ICP-MS (for semiconductor analysis, option # 200).
(Measurement condition)
A quartz torch and a coaxial PFA (perfluoroalkoxy alkane) nebulizer (for self-priming), and a quartz torch and a coaxial PFA (perfluoroalkoxy alkane) nebulizer (for self-priming) for measuring the content of metal atoms contained in the metal impurities in the treatment liquids prepared in each Example and Comparative Example. , Platinum interface cone was used. The measurement parameters of the cool plasma condition 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 a 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, while rotating the wafer at 50 rotations (rpm), the rinsing liquid (23 ° C.) was spray-discharged at a flow rate of 200 mL / min for 15 seconds to perform the rinsing treatment.
Finally, the wafer was dried at a high speed of 2500 rpm for 60 seconds. As the rinsing liquid, any of the treatment liquids S-1 to S-40 shown in Table 8 and Table 8-No. 2 was used. Table 9 and Table 9-2 show the rinse solutions used in each Example and Comparative Example. If there is no description of the rinsing liquid in Table 9 and Table 9-2, it means that the rinsing treatment has not been performed after the development.

〔Evaluation test〕
The performance of the exposed and developed wafers was evaluated for the following items. Details of the results are shown in Table 9 and Table 9-2.

(Evaluation of defect performance after development)
The number of particles having a diameter of 19 nm or more (hereinafter referred to as “defects”) existing on the surface of the wafer for evaluation of defects after development created above is measured by a wafer surface inspection device (SP-5; manufactured by KLA Tencor). After that, 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 an organic component without a metal component were defined as organic residues. The post-development defect evaluation of the metal particles and the post-development defect evaluation of the organic residue were evaluated based on the following criteria. The results are shown in the table below. 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": Number of defects is 200 or less "B": Number of defects is more than 200 and less than 500 "C": Number of defects is more than 500 and less than 1000 "D": Number of defects is more than 1000 and less than 1500 "E": Number of defects is Over 1500

(Line with roughness (LWR) performance evaluation)
When observing a line-and-space resist pattern resolved at the optimum exposure amount, when observing from the top of the pattern with a length-measuring scanning electron microscope (SEM (Hitachi Seisakusho S-9380II)), the line width is arbitrary. It was observed at the point of, and the measurement variation was evaluated by 3σ. The smaller the value, the better the performance.

2. ArF immersion exposure (Examples 2-1 to 2-47, Comparative Examples 2-1 to 2-6)
<ArF immersion exposure evaluation>
Using the resist composition shown in Table 5 above, a resist pattern was formed by the following operation.

[Applying 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 film thickness of 40 nm.
When performing L / S pattern evaluation, an organic antireflection film ARC29SR (manufactured by Brewer) is applied on a silicon wafer before the resist film is applied, and the film is baked at 205 ° C. for 60 seconds to achieve a film thickness of 86 nm. Antireflection film was formed.

[Applying the composition for forming an upper layer film and baking after coating (PB)]
For Examples 2-24 to 2-31, 2-33 to 2-35, the upper layer film forming composition (top coat composition) shown in Table 6 above was applied onto the resist film after baking, and then. , The PB temperature (unit: ° C.) shown in Tables 10 and 10-2 below was baked for 60 seconds to form an upper film (top coat) having a film thickness of 40 nm.

〔exposure〕
(Evaluation of defect performance after development)
Using an 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 produced above, 1 mJ / cm ² The entire surface was exposed without using a mask at the exposure amount of. Ultrapure water was used as the immersion liquid. Then, it was heated for 60 seconds (PEB: Post Exposure Bake) under the condition of 90 to 120 ° C. Then, using a developing device (manufactured by SOKUDO; RF ³ ), use the developing solutions shown in Tables 10 and 10-2 below (see Tables 8 and 8-Part 2 for each developing solution) 30. Paddle for seconds to develop, then rinse the wafer at 50 rpm for 15 seconds with the rinse solution shown in Tables 10 and 10-2 below, followed by 30 seconds at 2000 rpm. By rotating the wafer, a defect evaluation wafer in which the resist film was developed and removed over the entire surface of the wafer was prepared.

(Line with Roughness (LWR) evaluation)
An ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.750, inner sigma 0.650, Y deflection) was used on the wafer produced above to determine the dimensions on the wafer. Exposure to a line width of 80 nm and a space width of 40 nm via a 6% halftone mask containing a pattern (for L / S bridge evaluation) to form a line and space pattern with a pitch of 120 nm and a line width of 80 nm. In terms of quantity, pattern exposure was performed on the entire surface of the wafer. Ultrapure water was used as the immersion liquid. Then, heat for 60 seconds under the condition of 90 to 120 ° C. (PEB: Post Exposure)
Bake). Then, using a developing device (manufactured by SOKUDO; RF ³ ), paddle and develop with the developers shown in Tables 10 and 10-2 below for 30 seconds, and then rotate the wafer at 50 rpm. However, a line-and-space pattern was obtained by rinsing with the rinsing solution shown in Tables 10 and 10-2 below for 15 seconds, and then rotating the wafer at a rotation speed of 2000 rpm for 30 seconds.

〔Evaluation test〕
Similar to the above-mentioned "EUV exposure evaluation", the defect performance was evaluated and the line width roughness was evaluated. Details of the results are shown in Table 10 and Table 10-2.

3. 3. Evaluation Results As shown in the above Examples of Table 9, Table 9-Part 2, Table 10 and Table 10-Part 2, the SP value is in the range of 17 to 18.2 regardless of which exposure light source is used. A processing solution obtained by mixing a certain first organic solvent and a second organic solvent which is an organic solvent having an SP value of 16.3 MPa ^1/2 or more and an SP value ^{of not 17 to 18.2 MPa 1/2 is used.} If so, it was found that there were few post-development defects of the metal particles and post-development defects of the organic residue, and the performance was good. This is because by using a mixed developer with relatively high hydrophilicity, insoluble components such as resist polymer and metal impurities can be efficiently solvated, and reprecipitation in the developer is less likely to occur, resulting in defects. Is presumed to have been suppressed.

Further, it was found that the LWR performance was good when the above treatment liquid was used. The reason for this is not clear, but it is considered that the affinity of the developer with respect to the resin in the deprotected exposed portion is increased and the development occurs uniformly.

Further, it can be confirmed that the treatment liquid of the present invention is applicable to both negative type resin and positive type resin.

The treatment liquid according to the present invention is applied to a FluoroPure PFA composite drum (contact liquid inner surface; PFA resin lining) manufactured by Entegris and a steel drum can (contact liquid inner surface; zinc phosphate film) manufactured by JFE. Then, after storing at room temperature for 14 days, wet particles (residual defects remaining in the form of stains), organic impurity concentration analysis, and metal impurity concentration analysis were performed. , Entegris' FluoroPure PFA composite drum (inner surface of wetted liquid; PFA resin lining) was able to obtain better results.

10 Tank 20 Pump 32 1st metal ion adsorption filter 34 2nd metal ion adsorption filter 40 Filtration member 50 Distillation part 50 Organic impurity adsorption member 60 Supply pipe 100 Organic solvent purification device

Claims (38)

(A) A step of forming a resist film using a sensitive light beam or a radiation-sensitive composition, and
(B) The step of exposing the film and
(C) A pattern forming method including a step of treating the exposed film using a treatment liquid.
The treatment liquid contains 2 or more organic solvents having an SP value of 16.3 MPa ^{1/2 or more.}
Of the two or more organic solvents, at least one is ^{a ketone solvent having an SP value of 17 to 18.2 MPa 1/2} , butyl acetate, amyl acetate, pentyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate. , Hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, isobutyl isobutate, or butyl butate, and the two or more organic solvents are γ-butyrolactone, ethyl butyrate , amide solvent, or dimethylsulfoxide. including, pattern-shaped formation method. (A) A step of forming a resist film using a sensitive light beam or a radiation-sensitive composition, and
(B) The step of exposing the film and
(C) A pattern forming method including a step of treating the exposed film using a treatment liquid.
The treatment liquid contains 2 or more organic solvents having an SP value of 16.3 MPa ^{1/2 or more.}
Of the two or more organic solvents, at least one is ^{a ketone solvent having an SP value of 17 to 18.2 MPa 1/2} , and the two or more organic solvents are γ-butyrolactone, ethyl butyrate, an amide solvent, or , including dimethyl sulfoxide, pattern shape forming methods. (A) A step of forming a resist film using a sensitive light beam or a radiation-sensitive composition, and
(B) The step of exposing the film and
(C) A pattern forming method including a step of treating the exposed film using a treatment liquid.
The treatment liquid contains 2 or more organic solvents having an SP value of 16.3 MPa ^{1/2 or more.}
Of the two or more organic solvents, at least one is ^{a ketone solvent having an SP value of 17 to 18.2 MPa 1/2} , butyl acetate, amyl acetate, pentyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate. , Hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, isobutyl isobutate, or butyl butate, and the two or more organic solvents are γ-butyrolactone , ethyl butyrate, amide solvent, or dimethylsulfoxide. Pattern forming method including. The pattern forming method according to any one of claims 1 to 3 , wherein the step (b) is performed using a KrF or ArF excimer laser. The pattern forming method according to any one of claims 1 to 3 , wherein the step (b) is performed using EUV light. (A) A step of forming a resist film using a sensitive light beam or a radiation-sensitive composition, and
(B) A step of exposing the film with EUV light and
(C) A step of treating the exposed film with a treatment liquid
It is a pattern formation method including
The treatment liquid has an SP value of 16.3 MPa. ^1/2 Containing 2 or more of the above organic solvents,
Of the two or more organic solvents, at least one has an SP value of 17 to 18.2 MPa. ^1/2 Ketone solvent, butyl acetate, amyl acetate, pentyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, isobutyl isobutate, or butanoic acid. Butyl, and the above two or more organic solvents have an SP value of 20 MPa. ^1/2 The above ketone solvent, SP value is 20 MPa ^1/2 A pattern forming method containing the above ester solvent, amide solvent, or dimethyl sulfoxide. (A) A step of forming a resist film using a sensitive light beam or a radiation-sensitive composition, and
(B) A step of exposing the film with EUV light and
(C) A step of treating the exposed film with a treatment liquid
It is a pattern formation method including
The treatment liquid has an SP value of 16.3 MPa. ^1/2 Containing 2 or more of the above organic solvents,
Of the two or more organic solvents, at least one has an SP value of 17 to 18.2 MPa. ^1/2 The above 2 or more organic solvents have an SP value of 20 MPa. ^1/2 A pattern forming method containing the above organic solvent. (A) A step of forming a resist film using a sensitive light beam or a radiation-sensitive composition, and
(B) A step of exposing the film with EUV light and
(C) A step of treating the exposed film with a treatment liquid
It is a pattern formation method including
The treatment liquid has an SP value of 16.3 MPa. ^1/2 Containing 2 or more of the above organic solvents,
Of the two or more organic solvents, at least one has an SP value of 17 to 18.2 MPa. ^1/2 Ketone solvent, butyl acetate, amyl acetate, pentyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, isobutyl isobutate, or butanoic acid. A method for forming a pattern, which comprises butyl, and the two or more organic solvents include γ-butyrolactone, cyclohexanone, ethyl butyrate, an amide solvent, or dimethyl sulfoxide. The pattern forming method according to any one of claims 6 to 8 , wherein the ketone solvent is a solvent containing at least one selected from methyl isoamyl ketone, methyl isobutyl ketone, diisobutyl ketone and 2-heptanone. The pattern forming method according to any one of claims 1 to 9 , wherein the step (c) includes a step of developing the exposed film using the treatment liquid. The step (c) includes a step of developing the exposed film and a step of rinsing the developed film, and the treatment liquid is used in at least one of the developing step and the rinsing step. The pattern forming method according to any one of claims 1 to 9. (A) A step of forming a resist film using a sensitive light beam or a radiation-sensitive composition, and
(B) A step of exposing the film with EUV light and
(C) A pattern forming method including a step of treating the exposed film using a treatment liquid.
The treatment liquid contains 2 or more organic solvents having an SP value of 16.3 MPa ^{1/2 or more.}
Of the two or more organic solvents, at least one has an SP value of 17 to 18.2 MPa ^1/2 , and the two or more organic solvents have a SP value of 20 MPa 1/2 or more, a ketone solvent, and an SP value of ^1/2. 20 MPa ^1/2 or more ester solvents, amide solvents, or comprises dimethyl sulfoxide, pattern shape forming methods. The pattern forming method according to claim 12 , wherein the step (c) includes a step of developing the exposed film using the treatment liquid. The step (c) includes a step of developing the exposed film and a step of rinsing the developed film, and the treatment liquid is used in at least one of the developing step and the rinsing step. The pattern forming method according to claim 12. The pattern forming method according to any one of claims 12 to 14 , wherein the ester solvent is contained as the organic solvent having an SP value of 17 to 18.2. 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, isobutyl isobutate, and butyl butanoate. The pattern forming method according to claim 15 , which is a solvent containing at least one of these. The pattern forming method according to claim 16 , wherein the treatment liquid is used as a developing liquid for developing the exposed film. The pattern forming method according to any one of claims 12 to 14 , further comprising a ketone solvent as the organic solvent having an SP value of 17 to 18.2. The pattern forming method according to claim 18 , wherein the ketone solvent is a solvent containing at least one selected from methyl isoamyl ketone, methyl isobutyl ketone, diisobutyl ketone and 2-heptanone. The pattern forming method according to any one of claims 12 to 14 , which comprises at least one selected from 2-methylbutyl acetate, 1-methylbutyl acetate, and isoamyl acetate as the organic solvent having an SP value of 17 to 18.2. .. The pattern according to claim 20 , wherein the step (c) includes a step of developing the exposed film and a step of rinsing the developed film, and the treatment liquid is used in the rinsing step. Forming method. The pattern according to any one of claims 12 to 14 , which comprises at least one selected from PGME, γ-BL, NMP, DMSO, and ethyl butyrate as the organic solvent having an SP value other than 17 to 18.2. Forming method. The pattern according to claim 22 , wherein the step (c) includes a step of developing the exposed film and a step of rinsing the developed film, and the treatment liquid is used in the rinsing step. Forming method. The composition according to any one of claims 1 to 23 , which comprises a resin having a group which decomposes by the action of an acid to generate a polar group, and a compound which generates an acid by irradiation with active light or radiation. Pattern formation method. (D) The pattern forming method according to any one of claims 1 to 24 , further comprising heating the film treated with the treatment liquid. The pattern forming method according to any one of claims 1 to 25 , which contains 0.001 to 30 mass ppm of organic impurities having a boiling point of 300 ° C. or higher with respect to the total mass of the treatment liquid. The treatment liquid contains at least one 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. The pattern forming method according to any one of claims 1 to 26. The treatment liquid contains at least one element selected from the group consisting of Fe, Cr, Ni and Pb, and the total amount of the elements is 0.001 to 100 mass ppt with respect to the total mass of the treatment liquid. The pattern forming method according to any one of claims 1 to 27. The treatment liquid used in the pattern forming method according to claim 1, which contains 2 or more organic solvents having an ^{SP value of 16.3 MPa 1/2 or more.}
Of the two or more organic solvents, at least one is ^{a ketone solvent having an SP value of 17 to 18.2 MPa 1/2} , butyl acetate, amyl acetate, pentyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate. , Hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, isobutyl isobutate, or butyl butate, and the two or more organic solvents are γ-butyrolactone, ethyl butyrate , amide solvent, or dimethylsulfoxide. Containing, processing solution. The treatment liquid used in the pattern forming method according to claim 2, which contains 2 or more organic solvents having an ^{SP value of 16.3 MPa 1/2 or more.}
Of the two or more organic solvents, at least one is ^{a ketone solvent having an SP value of 17 to 18.2 MPa 1/2} , and the two or more organic solvents are γ-butyrolactone, ethyl butyrate, an amide solvent, or , A treatment solution containing dimethyl sulfoxide. The treatment liquid used in the pattern forming method according to claim 3, which contains 2 or more organic solvents having an ^{SP value of 16.3 MPa 1/2 or more.}
Of the two or more organic solvents, at least one is ^{a ketone solvent having an SP value of 17 to 18.2 MPa 1/2} , butyl acetate, amyl acetate, pentyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate. , Hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, isobutyl isobutate, or butyl butate, and the two or more organic solvents are γ-butyrolactone , ethyl butyrate, amide solvent, or dimethylsulfoxide. Containing, processing solution. The treatment liquid used in the pattern forming method according to claim 12 , which contains 2 or more organic solvents having an ^{SP value of 16.3 MPa 1/2 or more.}
Of the two or more organic solvents, at least one has an SP value of 17 to 18.2 MPa ^1/2 , and the two or more organic solvents have a SP value of 20 MPa 1/2 or more, a ketone solvent, and an SP value of ^1/2. A treatment liquid containing an ester solvent, an amide solvent, or dimethyl sulfoxide of 20 MPa ^{1/2 or more.} The treatment liquid according to any one of claims 29 to 32, which is used for developing an exposed film. The treatment liquid according to any one of claims 29 to 32, which is used for rinsing the developed film. The treatment liquid according to any one of claims 29 to 34 , which contains 0.001 to 30 mass ppm of organic impurities having a boiling point of 300 ° C. or higher with respect to the total mass of the treatment liquid. The treatment liquid contains at least one 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. The treatment liquid according to any one of claims 29 to 35. Claim that the treatment liquid contains at least one element selected from the group consisting of Fe, Cr, Ni and Pb, and the total amount of the elements is 0.001 to 100 mass ppt with respect to the total mass of the treatment liquid. Item 2. The treatment liquid according to any one of Items 29 to 36. The method for producing a treatment liquid according to any one of claims 29 to 37 , wherein the treatment liquid is produced through distillation and / or filtration.

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