JP6607940B2 - Pattern forming method and electronic device manufacturing method - Google Patents

Description

The present invention relates to a pattern forming method, an electronic device manufacturing method, and an electronic device.
More specifically, the present invention relates to a pattern forming method used for a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal and a thermal head, and a lithography process for other photofabrication, and the pattern formation. The present invention relates to a method for manufacturing an electronic device including the method.

Conventionally, in a manufacturing process of a semiconductor device such as an IC (Integrated Circuit) or an LSI (Large Scale Integrated Circuit), fine processing by lithography using a photoresist composition has been performed. In recent years, with the high integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quarter micron region has been required. Along with this, exposure has been conventionally performed using g-line, but now it is performed using i-line and further KrF excimer laser light, and there is a tendency to shorten the wavelength. It is done. Further, in addition to excimer laser light, lithography using electron beams, X-rays, or EUV light (Extreme Ultra Violet) has also been developed.
In such lithography, after forming a film with a photoresist composition (also called actinic ray-sensitive or radiation-sensitive composition), the resulting film is developed with a developer, or the developed film is rinsed. It is done to wash with.
For example, Patent Document 1 describes a pattern forming method using a developer containing an organic solvent and a rinse liquid containing an organic solvent.

JP 2013-257379 A

In recent years, in order to manufacture highly integrated and highly accurate electronic devices, a method for stably forming a fine pattern with high accuracy (for example, a line width of 20 nm or less) is required.
However, as miniaturization progresses, not only pattern collapse but also the occurrence of bridges due to the reduction in the space width between lines has become more prominent. In addition, the effect of the line width uniformity within the wafer surface (CDU) has become significant.

  The present invention has been made in view of the above points, and has a pattern with excellent pattern collapse performance and bridge performance, and CDU (Critical Dimension Uniformity) in a fine pattern with high accuracy (for example, a line width of 20 nm or less). An object of the present invention is to provide a forming method, an electronic device manufacturing method including the pattern forming method, and an electronic device manufactured by the electronic device manufacturing method.

As a result of intensive studies on the above problems, the present inventors have used a developer containing an organic solvent having a Hansen solubility parameter δp of 2.9 or more and 5 or less, and at least one of fluorine atoms and silicon atoms. It has been found that a desired effect can be obtained by using a rinsing liquid containing an organic solvent containing one.
Although the detailed reason is not certain, the present inventors presume as follows. Since carbon-fluorine bonds and carbon-silicon bonds generally have low polarizability and weak intermolecular forces, they generally have low surface tension. Thus, it is considered that pattern collapse due to capillary force could be suppressed. On the other hand, regarding bridge and CDU, although it cannot be explained by capillary force, an organic solvent having Hansen solubility parameter δp in the range of 2.9 to 5 and an organic solvent containing at least one of fluorine atom and silicon atom It is considered that the miscibility of the CD was improved, thereby improving the rinsing efficiency and suppressing the CD variation and bridging caused by the unevenness and variation of the rinse.
More specifically, the present inventors have found that the above object can be achieved by the following configuration.
[1]
Resist film formation using an actinic ray-sensitive or radiation-sensitive composition containing a resin whose solubility in an organic solvent is reduced by the action of an acid and a compound that generates acid by actinic rays or radiation. Process,
An exposure step of exposing the resist film;
Developing the exposed resist film with a developer containing 60% by mass or more of an organic solvent having a Hansen solubility parameter δp of 2.9 to 5 with respect to the total mass of the developer;
Rinsing the developed resist film with a rinsing liquid containing 30% by mass or more of an organic solvent (excluding aromatic compounds) containing at least one of fluorine atoms and silicon atoms with respect to the total mass of the rinsing liquid When,
The pattern formation method which has these in order.
[ 2 ]
Resist film formation using an actinic ray-sensitive or radiation-sensitive composition containing a resin whose solubility in an organic solvent is reduced by the action of an acid and a compound that generates acid by actinic rays or radiation. Process,
An exposure step of exposing the resist film;
Developing the exposed resist film with a developer containing an organic solvent having a Hansen solubility parameter δp of 2.9 to 5;
Rinsing the developed resist film with a rinsing liquid containing an organic solvent containing at least one of a fluorine atom and a silicon atom, in this order, and a pattern forming method comprising:
The pattern formation method whose content of the said organic solvent contained in the said rinse liquid is 100 mass% with respect to the total mass of the said rinse liquid.
[ 3 ]
The pattern forming method according to [1] or [2] , wherein the organic solvent contained in the rinse liquid is a hydrocarbon solvent or an ether solvent containing at least one of a fluorine atom and a silicon atom.
[ 4 ]
The pattern formation method according to any one of [1] to [ 3 ], wherein the organic solvent contained in the rinse liquid contains a fluorine atom.
[ 5 ]
The pattern forming method according to [ 4 ], wherein the organic solvent contained in the rinse liquid is at least one selected from hydrofluoroether, perfluorocarbon, and hydrofluorocarbon.
[ 6 ]
The pattern forming method according to [ 4 ] or [ 5 ], wherein the organic solvent contained in the rinse liquid is at least one selected from perfluorocarbon and hydrofluorocarbon.
[ 7 ]
The pattern forming method according to any one of [1] to [ 6 ], wherein the organic solvent contained in the developer is an ester solvent.
[ 8 ]
The pattern forming method according to any one of [1] to [ 7 ], wherein the organic solvent contained in the developer is an organic solvent having 6 to 10 carbon atoms.
[ 9 ]
The organic solvent contained in the developer is butyl acetate, pentyl acetate, hexyl acetate, heptyl acetate, isobutyl acetate, isopentyl acetate, isohexyl acetate, secbutyl acetate, tertbutyl acetate, butyl butanoate, 2-ethylhexyl acetate. The pattern formation method according to any one of [1] to [ 8 ], which is at least one selected.
[ 10 ]
The pattern formation method according to any one of [1] to [ 9 ], wherein the exposure is performed using an electron beam or extreme ultraviolet rays.
[ 11 ]
The manufacturing method of an electronic device containing the pattern formation method of any one of [1]-[ 10 ].
The present invention relates to the above [1] to [ 11 ], but other matters are also described in this specification for reference.

<1>
A resist film forming step of forming a resist film using an actinic ray-sensitive or radiation-sensitive composition;
An exposure step of exposing the resist film;
Developing the exposed resist film with a developer containing an organic solvent having a Hansen solubility parameter δp of 2.9 to 5;
Rinsing the developed resist film with a rinsing liquid containing an organic solvent containing at least one of fluorine atoms and silicon atoms;
The pattern formation method which has these in order.
<2>
The pattern formation method as described in <1> whose content of the said organic solvent contained in the said rinse liquid is 10 mass% or more with respect to the total mass of the said rinse liquid.
<3>
The pattern formation method as described in <1> or <2> whose content of the said organic solvent contained in the said rinse liquid is 30 mass% or more with respect to the total mass of the said rinse liquid.
<4>
The pattern according to any one of <1> to <3>, wherein the organic solvent contained in the rinse liquid is a hydrocarbon solvent or an ether solvent containing at least one of a fluorine atom and a silicon atom. Forming method.
<5>
The pattern formation method according to any one of <1> to <4>, wherein the organic solvent contained in the rinse liquid contains a fluorine atom.
<6>
The pattern forming method according to <5>, wherein the organic solvent contained in the rinse liquid is at least one selected from hydrofluoroether, perfluorocarbon, and hydrofluorocarbon.
<7>
The pattern forming method according to <5> or <6>, wherein the organic solvent contained in the rinse liquid is at least one selected from perfluorocarbon and hydrofluorocarbon.
<8>
The pattern formation method according to any one of <1> to <7>, wherein the organic solvent contained in the developer is an ester solvent.
<9>
The pattern forming method according to any one of <1> to <8>, wherein the organic solvent contained in the developer is an organic solvent having 6 to 10 carbon atoms.
<10>
The organic solvent contained in the developer is butyl acetate, pentyl acetate, hexyl acetate, heptyl acetate, isobutyl acetate, isopentyl acetate, isohexyl acetate, secbutyl acetate, tertbutyl acetate, butyl butanoate, 2-ethylhexyl acetate. The pattern formation method according to any one of <1> to <9>, which is at least one selected.
<11>
The pattern formation method according to any one of <1> to <10>, wherein the exposure is performed using an electron beam or extreme ultraviolet rays.
<12>
<1>-<11> The manufacturing method of an electronic device containing the pattern formation method of any one of <11>.

  According to the present invention, in a fine pattern with high accuracy (for example, a line width of 20 nm or less), a pattern forming method with excellent pattern collapse performance and bridge performance, and CDU, and a method for manufacturing an electronic device including the pattern forming method, An electronic device manufactured by this electronic device manufacturing method can be provided.

Below, an example of the form for implementing this invention is demonstrated.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays, X-rays, electron beams, and the like. In the present invention, “light” means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not limited to exposure to deep ultraviolet rays such as mercury lamps and excimer lasers, X-rays, extreme ultraviolet rays (EUV light), etc., but also EB (electron beams) and ions. Drawing with particle beams such as beams is also included in exposure.
In addition, in the description of a group (atomic group) in this specification, the description which does not describe substitution or unsubstituted includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, "(meth) acrylic monomer" means at least one monomer having the structure of _"CH 2 = _CH-CO-" or _{"CH 2 = C (CH 3)} -CO- " To do. Similarly, “(meth) acrylate” and “(meth) acrylic acid” mean “at least one of acrylate and methacrylate” and “at least one of acrylic acid and methacrylic acid”, respectively.
In the present specification, the weight average molecular weight of the resin is a polystyrene equivalent value measured by a GPC (gel permeation chromatography) method. GPC uses HLC-8120 (manufactured by Tosoh Corporation), TSK gel Multipore HXL-M (manufactured by Tosoh Corporation, 7.8 mm ID × 30.0 cm) as a column, and THF (tetrahydrofuran) as an eluent. You can follow the same method.

<Pattern formation method>
The pattern forming method of the present invention comprises:
A resist film forming step of forming a resist film using an actinic ray-sensitive or radiation-sensitive composition;
An exposure step of exposing the resist film;
Developing the exposed resist film using a developer containing an organic solvent;
Rinsing the developed resist film with a rinsing liquid containing an organic solvent;
In this order,
The developer contains an organic solvent having a Hansen solubility parameter δp of 2.9 to 5,
It is a pattern formation method in which the said rinse liquid contains the organic solvent containing at least one of a fluorine atom and a silicon atom.

  Hereinafter, each process which the pattern formation method of this invention has is demonstrated.

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

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

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

The 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 with a line width of 20 nm or less, the thickness of the resist film to be formed is preferably 50 nm or less. If the film thickness is 50 nm or less, pattern collapse is less likely to occur when a development step described later is applied, and better resolution performance is obtained.
More preferably, the film thickness ranges from 15 nm to 45 nm. If the film thickness is 15 nm or more, sufficient etching resistance can be obtained. More preferably, the film thickness ranges from 15 nm to 40 nm. When the film thickness is within this range, etching resistance and better resolution performance can be satisfied at the same time.

In the pattern forming method of the present invention, a top coat may be formed on the upper layer of the resist film. It is preferable that the top coat is not mixed with the resist film and can be uniformly applied to the upper layer of the resist film.
The top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. For example, the top coat can be formed based on the description in paragraphs 0072 to 0082 of JP-A No. 2014-059543.
In the development step, for example, a top coat containing a basic compound as described in JP2013-61648A is preferably formed on the resist film. Specific examples of the basic compound that can be contained in the top coat will be described later as the basic compound (E).
The top coat 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.

<Exposure process>
The exposure step is a step of exposing the resist film, and can be performed, for example, by the following method.
The resist film formed as described above is irradiated with actinic rays or radiation through a predetermined mask. Note that in electron beam irradiation, drawing (direct drawing) without using a mask is common.
Although it does not specifically limit as actinic light or radiation, For example, they are KrF excimer laser, ArF excimer laser, extreme ultraviolet (EUV, Extreme Ultra Violet), an electron beam (EB, Electron Beam), etc., Extreme ultraviolet or an electron beam is especially preferable. . The exposure may be immersion exposure.

<Bake>
In the pattern forming method of the present invention, baking (heating) is preferably performed after exposure and before development. The reaction of the exposed part is promoted by baking, and the sensitivity and pattern shape become better.
The heating temperature is preferably 80 to 150 ° C, more preferably 80 to 140 ° C, and still more preferably 80 to 130 ° C.
The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and still more preferably 60 to 600 seconds.
Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.

<Development process>
The development step is a step of developing the exposed resist film with a developer.

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

<Developer>
The developer in the present invention contains an organic solvent having a Hansen solubility parameter δp of 2.9 or more and 5 or less. In addition, since the developing solution in this invention contains the organic solvent, it can also be called organic developing solution.

As the organic solvent used in the developer, an organic solvent having a Hansen solubility parameter δp of 2.9 or more and 5 or less is used.
If the value of δp is smaller than 2.9, the affinity for the resist film is insufficient and development does not proceed. On the other hand, if the value of δp is larger than 5, the polarity of the developer is too high, the compatibility with the rinsing liquid containing an organic solvent containing at least one of fluorine atom and silicon atom in the present invention is insufficient, and CDU is low. Getting worse.

  As the Hansen solubility parameter δp, the value described in “Hansen Solubility Parameters: A User's Handbook, Second Edition” (Charles M. Hansen, 2007) was used.

Various organic solvents are widely used as the organic solvent having a Hansen solubility parameter δp of 2.9 or more and 5 or less. For example, a solvent such as an ester solvent, a ketone solvent, or an ether solvent is used. Can do. Among them, an ester solvent having a Hansen solubility parameter δp of 2.9 or more and 5 or less is preferable.
In addition, the value of δp is preferably 2.9 to 4.0, and more preferably 2.9 to 3.5.

  In the present invention, the ester solvent is a solvent having an ester bond in the molecule, the ketone solvent is a solvent having a ketone group in the molecule, and the ether solvent is an ether bond in the molecule. It is a solvent having Among these, there is a solvent having a plurality of types of the above functional groups in one molecule. In this case, it is applicable to any solvent type including the functional group of the solvent.

  The organic solvent having a Hansen solubility parameter δp of 2.9 or more and 5 or less is preferably an organic solvent having 6 to 10 carbon atoms from the viewpoint of affinity with the rinsing liquid, and has 6 to 9 carbon atoms. The organic solvent is more preferably an organic solvent having 7 to 9 carbon atoms.

Examples of ester solvents are shown below. The numbers in parentheses indicate the value of Hansen's solubility parameter δp.
Propyl acetate (4.3), butyl acetate (3.7), pentyl acetate (3.3), hexyl acetate (2.9), heptyl acetate (2.9), isopropyl acetate (4.5), isobutyl acetate (3.7), isopentyl acetate (3.1), isohexyl acetate (3.1), secbutyl acetate (3.7), tertbutyl acetate (3.7), butyl butanoate (2.9), acetic acid 2-methylbutyl (3.1), 1-methylbutyl acetate (3.1)
Among these, ester solvents having 6 to 10 carbon atoms are particularly preferably used. Specifically, butyl acetate (3.7), pentyl acetate (3.3), hexyl acetate (2.9), heptyl acetate (2.9), isobutyl acetate (3.7), isopentyl acetate (3. 1), isohexyl acetate (3.1), sec butyl acetate (3.7), tert butyl acetate (3.7), butyl butanoate (2.9), 2-ethylhexyl acetate (2.9), It is preferable that they are at least one of these.

  Examples of the ketone solvent include diisobutyl ketone (3.7) and methyl isobutyl ketone (3.8).

  Examples of the ether solvent include diethyl ether (2.9), diisopropyl ether (3.2), and dibutyl ether (2.9).

  The developer may contain only one kind of organic solvent having a Hansen solubility parameter δp of 2.9 or more and 5 or less, or may contain two or more kinds.

  The vapor pressure of the developer (the vapor pressure as a whole in the case of a mixed solvent) is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the developing solution to 5 kPa or less, evaporation of the developing solution on the substrate or in the developing cup is suppressed, temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface is improved. It improves.

  In the developer, the component containing sulfur atoms is preferably 10 mmol / L or less.

Examples of organic solvents that may be used in combination with an organic solvent having a Hansen solubility parameter δp of 2.9 or more and 5 or less in the developer include the following organic solvents.
Examples of ester solvents that the developer may contain include methyl acetate, ethyl acetate, octyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), Ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, Diethylene glycol monobutyl ether Acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monoethyl Ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl- 3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl Ru-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate Propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, pentyl propionate, hexyl propionate, heptyl propionate, butane Isobutyl acid, pentyl butanoate, hexyl butanoate, isobutyl isobutanoate, propyl pentanoate, isopropyl pentanoate, butyl pentanoate, pentyl pentanoate, ethyl hexanoate, hexa Propylate, butyl hexanoate, isobutyl hexanoate, methyl heptanoate, ethyl heptanoate, propyl heptanoate, cyclohexyl acetate, cycloheptyl acetate, cyclopentyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl Examples include -3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, and the like.

  Examples of the ketone solvent that the developer may contain include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate, and γ-butyrolactone.

  Examples of ether solvents that the developer may contain include glycol ether solvents that do not contain hydroxyl groups such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether, aromatic ether solvents such as anisole and phenetole, Examples include dioxane, tetrahydrofuran, tetrahydropyran, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane and the like.

  Examples of the alcohol solvent that the developer may contain include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, and 1-pen. Tanol, 2-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-decanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol 3-methyl-3-pentanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3- Methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl- -Pentanol, 4-methyl-3-pentanol, cyclohexanol, 5-methyl-2-hexanol, 4-methyl-2-hexanol, 4,5-dityl-2-hexal, 6-methyl-2-heptanol, Alcohols (monohydric alcohols) such as 7-methyl-2-octanol, 8-methyl-2-nonal, 9-methyl-2-decanol, 3-methoxy-1-butanol, ethylene glycol, diethylene glycol, triethylene glycol Glycol solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol), diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbutanol, ethyl And glycol ether solvents containing hydroxyl groups such as ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monophenyl ether, and the like. . Among these, it is preferable to use a glycol ether solvent.

  Examples of the amide solvent that may be contained in the developer include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl. -2-Imidazolidinone can be used.

  Examples of hydrocarbon solvents that the developer may contain include pentane, hexane, octane, nonane, decane, dodecane, undecane, hexadecane, 2,2,4-trimethylpentane, and 2,2,3-trimethylhexane. , Aliphatic hydrocarbon solvents such as perfluorohexane and perfluoroheptane, toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, Aromatic hydrocarbon solvents such as ethyldimethylbenzene and dipropylbenzene, and unsaturated hydrocarbon solvents such as octene, nonene, decene, undecene, dodecene, and hexadecene.

The unsaturated hydrocarbon solvent may have a plurality of double bonds and triple bonds, and may be present at any position of the hydrocarbon chain. Cis and trans isomers having a double bond may be mixed.
The aliphatic hydrocarbon solvent that is a hydrocarbon solvent may be a mixture of compounds having the same number of carbon atoms and different structures. For example, when decane is used as the aliphatic hydrocarbon solvent, 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and isodecane, which are compounds having the same carbon number and different structures, are aliphatic hydrocarbon solvents. May be included.
Moreover, only 1 type may be contained and the compound of the structure from which the said same carbon number differs differs may be contained.

  The content of the organic solvent having a Hansen solubility parameter δp in the developer of 2.9 or more and 5 or less is preferably 60% by mass or more, more preferably 80% by mass or more based on the total mass of the developer. More preferably, it is more preferably 90% by mass or more, and particularly preferably 95% by mass or more. Pattern collapse performance is further improved by setting the content of the organic solvent having a Hansen solubility parameter δp of 2.9 to 5 in the developer to 60% by mass or more.

  When the developer contains an organic solvent having a Hansen solubility parameter δp of 2.9 or more and 5 or less, the developer contains a solvent other than the organic solvent having a Hansen solubility parameter δp of 2.9 or more and 5 or less. The amount is preferably 40% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and particularly preferably 5% by mass or less with respect to the total mass of the developer.

The developer preferably contains a surfactant. Thereby, the wettability with respect to the resist film is improved, the developability is improved, and the generation of foreign matters tends to be suppressed.
As the surfactant, the same surfactants as those used in the actinic ray-sensitive or radiation-sensitive composition described later can be used.
When a developing solution contains surfactant, it is preferable that content of surfactant is 0.001-5 mass% with respect to the total mass of a developing solution, More preferably, 0.005-2 mass %, And more preferably 0.01 to 0.5% by mass.

  The developer preferably contains an antioxidant. Thereby, generation | occurrence | production of an oxidizing agent with time can be suppressed and content of an oxidizing agent can be reduced more.

As the antioxidant, known ones can be used, but when used for semiconductor applications, amine-based antioxidants and phenol-based antioxidants are preferably used.
Examples of amine-based antioxidants include 1-naphthylamine, phenyl-1-naphthylamine, p-octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, p-dodecylphenyl-1-naphthylamine, and phenyl-2. -Naphthylamine antioxidants such as naphthylamine; N, N'-diisopropyl-p-phenylenediamine, N, N'-diisobutyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N ' -Di-β-naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-1,3-dimethylbutyl-N '-Phenyl-p-phenylenediamine, dioctyl-p-phenyle Phenylenediamine-based antioxidants such as diamine, phenylhexyl-p-phenylenediamine, phenyloctyl-p-phenylenediamine; dipyridylamine, diphenylamine, p, p′-di-n-butyldiphenylamine, p, p′-di- t-butyldiphenylamine, p, p'-di-t-pentyldiphenylamine, p, p'-dioctyldiphenylamine, p, p'-dinonyldiphenylamine, p, p'-didecyldiphenylamine, p, p'-didodecyl Diphenylamine oxidation such as diphenylamine, p, p'-distyryldiphenylamine, p, p'-dimethoxydiphenylamine, 4,4'-bis (4-α, α-dimethylbenzoyl) diphenylamine, p-isopropoxydiphenylamine, dipyridylamine Inhibitor; phenothiazi And phenothiazine antioxidants such as N-methylphenothiazine, N-ethylphenothiazine, 3,7-dioctylphenothiazine, phenothiazinecarboxylic acid ester and phenoselenadine.
Examples of phenolic antioxidants include 2,6-di-tert-butylphenol (hereinafter, tertiary butyl is abbreviated as t-butyl), 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-tert-butylphenol), 4,4′-bis (2,6-di-tert-butylphenol), 4,4′-bis (2-methyl-6-tert-butylphenol), 2,2 '-Methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol) 4,4′-isopropylidenebis (2,6-di-t-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis (4-methyl-6- Nonylphenol), 2,2'-isobutylidenebis (4,6-dimethylphenol), 2,6-bis (2'-hydroxy-3'-t-butyl-5'-methylbenzyl) -4-methylphenol , 3-t-butyl-4-hydroxyanisole, 2-t-butyl-4-hydroxyanisole, octyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- (4- Hydroxy-3,5-di-t-butylphenyl) stearyl propionate, oleyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- (4 Hydroxy-3,5-di-t-butylphenyl) dodecylpropionate, decyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- (4-hydroxy-3,5- Octyl di-t-butylphenyl) propionate, tetrakis {3- (4-hydroxy-3,5-di-t-butylphenyl) propionyloxymethyl} methane, 3- (4-hydroxy-3,5-di-) t-butylphenyl) propionic acid glycerin monoester, ester of 3- (4-hydroxy-3,5-di-t-butylphenyl) propionic acid and glycerin monooleyl ether, 3- (4-hydroxy-3,5 -Di-t-butylphenyl) propionic acid butylene glycol diester, 3- (4-hydroxy-3,5-di-t-butylpheny ) Propionic acid thiodiglycol diester, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (2-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-α-dimethylamino-p-cresol, 2,6-di-t-butyl-4- (N, N′-dimethyl) Aminomethylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, tris {(3,5-di-tert-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) i Sosocyanurate, bis {2-methyl-4- (3-n-alkylthiopropionyloxy) -5-tert-butylphenyl} sulfide, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6 -Dimethylbenzyl) isocyanurate, tetraphthaloyl-di (2,6-dimethyl-4-tert-butyl-3-hydroxybenzylsulfide), 6- (4-hydroxy-3,5-di-tert-butylanilino)- 2,4-bis (octylthio) -1,3,5-triazine, 2,2-thio- {diethyl-bis-3- (3,5-di-t-butyl-4-hydroxyphenyl)} propionate, N , N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 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 and the like.

  Although content of antioxidant is not specifically limited, 0.0001-1 mass% is preferable with respect to the total mass of a developing solution, 0.0001-0.1 mass% is more preferable, 0.0001-0 More preferred is 0.01 mass%. 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, development residue tends to be suppressed.

The developer preferably contains a basic compound. Specific examples of the basic compound include compounds exemplified as basic compounds that can be contained in the actinic ray-sensitive or radiation-sensitive composition described later.
Among the basic compounds that can be contained in the developer, a nitrogen-containing compound can be preferably used.

  As the developer used in the development step, development with an alkali developer (so-called double development) may be performed in addition to the development using the developer described above.

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

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

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

<Rinse solution>
The rinse liquid in the present invention contains an organic solvent containing at least one of a fluorine atom and a silicon atom. In addition, since the rinse liquid in this invention contains the organic solvent, it can also be called organic type rinse liquid.

  The vapor pressure of the rinsing liquid (the vapor pressure as a whole in the case of a mixed solvent) is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and 0.12 kPa or more at 20 ° C. Most preferably, it is 3 kPa or less. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

As the organic solvent containing at least one of a fluorine atom and a silicon atom contained in the rinsing liquid, a hydrocarbon solvent or an ether solvent containing at least one of a fluorine atom and a silicon atom is preferable.
As the organic solvent containing at least one of a fluorine atom and a silicon atom, an organic solvent containing a fluorine atom is preferable.
Examples of the organic solvent containing at least one of a fluorine atom and a silicon atom include hydrofluoroether, perfluorocarbon, and hydrofluorocarbon, preferably at least one selected from these, and selected from perfluorocarbon and hydrofluorocarbon. More preferably, it is at least one.

(Hydrofluoroether)
Hydrofluoroether (HFE) is not particularly limited, but is preferably a compound represented by the following formula 1.
Formula 1 R1-O-R2
In Formula 1, R1 represents an alkyl group or fluoroalkyl group having 1 to 12 carbon atoms, and R2 represents a perfluoroalkyl group or fluoroalkyl group having 1 to 12 carbon atoms.
R1 and R2 preferably represent a perfluoroalkyl group or a fluoroalkyl group having 3 to 12 carbon atoms.

Specific examples of the hydrofluoroether include methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, and HFE-347pc-f (CF ₃ CH ₂ OCF ₂ CHF ₂ ). Specific products include Asahi Clin AE-3000 (Asahi Glass), Novec HFE-7100 (Sumitomo 3M), Novec HFE-7200 (Sumitomo 3M) and the like.
A hydrofluoroether may be used individually by 1 type, and 2 or more types may be mixed and used for it.

(Perfluorocarbon)
Perfluorocarbon (PFC) is a fully fluorinated alkyl compound, and it does not matter whether it is linear, branched or cyclic. The range of the number of carbon atoms of the perfluorocarbon is preferably 3-12. When the number of carbon atoms is small, the volatility is too high, so that the temperature uniformity within the wafer surface deteriorates. On the other hand, when the number of carbon atoms is large, the volatility is too low, so that even if spin drying after rinsing is performed, the solvent does not volatilize and remains, and it becomes difficult to obtain the original purpose of rinsing.

Specific examples of perfluorocarbon that can be used in the present invention include perfluorobutane, perfluoropentane, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorononane, and perfluorodecane. Specific products include Fluorinert FC-770 (Sumitomo 3M), Flutec (Rhone Plan), Galden (Audimont), Al-Food (Asahi Glass) and the like.
Perfluorocarbons may be used singly or in combination of two or more.

(Hydrofluorocarbon)
Hydrofluorocarbons (HFCs) are compounds in which some of the hydrogen atoms in the hydrocarbons become fluorine atoms, regardless of whether they are linear, branched or cyclic, and there are at least one fluorine atom in the compound molecule. To do. The number of carbon atoms in the hydrofluorocarbon is preferably 3-12. If the number of carbon atoms is 3 or more, the volatility is not too high and the temperature uniformity in the wafer surface is improved. On the other hand, if the number of carbon atoms is 12 or less, the volatility is not too low, and the solvent is easily volatilized by spin-drying after rinsing.

Examples of _{hydrofluorocarbon, HFC-52-13p (CF 3 CF} 2 CF 2 CF 2 CF 2 CHF 2), HFC-569sf (CF 3 CF 2 CF 2 CF 2 CH 2 CH 3), HFC-43- 10 mee, 1,1,1,3,3 pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane and the like can be mentioned. Specific products include Bertrell (Mitsui / DuPont Fluorochemical), Solcan 365mfc (Solvay), Asahi Clin AC-2000 (Asahi Glass), Asahi Clin AC-4000 (Asahi Glass), Asahi Clin AC-6000 (Asahi Glass), and the like. can give.
Hydrofluorocarbons may be used singly or in combination of two or more.

Examples of the organic solvent containing silicon atoms contained in the rinse liquid include siloxane solvents.
Examples of the siloxane solvent include chain siloxane solvents such as hexamethyldisiloxane, octamethyltrisiloxane, and decamethyltetrasiloxane. Among these, preferred are hexamethyldisiloxane and octamethyltrisiloxane.

  Although there is no restriction | limiting in particular in content of the organic solvent containing at least one of a fluorine atom and a silicon atom contained in a rinse liquid, It is preferable that it is 10 mass% or more with respect to the total mass of a rinse liquid, and 30 mass% More preferably, it is more preferably 50% by mass or more, and most preferably 100% by mass.

  The organic solvent containing at least one of a fluorine atom and a silicon atom may be used alone, a plurality of types may be mixed, or an organic solvent other than an organic solvent containing at least one of a fluorine atom and a silicon atom. You may mix with an organic solvent (it is also called "other organic solvents").

  The other organic solvent that the rinsing liquid may contain is at least one selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. An organic solvent is mentioned. Specific examples of these organic solvents are the same as those described for the developer.

When mixed with an organic solvent other than an organic solvent containing at least one of a fluorine atom and a silicon atom, the content of the organic solvent other than the organic solvent containing at least one of a fluorine atom and a silicon atom is the total mass of the rinsing liquid. On the other hand, 40 mass% or less is preferable, More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less, Most preferably, it is 5 mass% or less.
By setting the content of the organic solvent other than the organic solvent containing at least one of a fluorine atom and a silicon atom to 40% by mass or less, good pattern collapse characteristics can be obtained.

  In the rinse liquid, the component containing sulfur atoms is preferably 10 mmol / L or less.

The rinse liquid may contain a surfactant. Thereby, the wettability with respect to the resist film is improved, the rinsing property is improved, and the generation of foreign matters tends to be suppressed.
As the surfactant, the same surfactants as those used in the actinic ray-sensitive or radiation-sensitive composition described later can be used.
The content of the surfactant is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, and still more preferably 0.01 to 0.5% with respect to the total mass of the rinse liquid. % By mass.

  It is preferable that the rinse liquid contains an antioxidant. Thereby, generation | occurrence | production of an oxidizing agent with time can be suppressed and deterioration of a liquid with time can be suppressed. Specific examples of the antioxidant are the same as the specific examples of the antioxidant that the developer may contain.

  When the rinse liquid contains an antioxidant, the content of the antioxidant is not particularly limited, but is preferably 0.0001 to 1% by mass, 0.0001 to 0.1% with respect to the total mass of the rinse liquid. % By mass is more preferable, and 0.0001 to 0.01% by mass is even more preferable.

<Actinic ray-sensitive or radiation-sensitive composition>
Next, the actinic ray-sensitive or radiation-sensitive composition used in the pattern forming method of the present invention will be described.
In the pattern forming method of the present invention, the actinic ray-sensitive or radiation-sensitive composition (also referred to as “resist composition”) is an actinic ray-sensitive or radiation-sensitive material for organic solvent development using a developer containing an organic solvent. It is preferable that it is a composition. Here, the term “for organic solvent development” means an application that is used in a step of developing using a developer containing at least an organic solvent. The actinic ray-sensitive or radiation-sensitive composition in the present invention may be a chemically amplified resist composition or a non-chemically amplified resist composition, but preferably a chemically amplified resist composition. . In addition, the actinic ray-sensitive or radiation-sensitive composition in the present invention may be a positive resist composition or a negative resist composition.
The radiation-sensitive or actinic ray-sensitive composition in the present invention is preferably used for electron beam or extreme ultraviolet exposure.

Actinic ray-sensitive or radiation-sensitive composition in the present invention, and various materials used in the pattern forming method of the present invention (for example, a resist solvent, a developer, a rinse solution, a composition for forming an antireflection film, a top coat) The composition for forming) is preferably free of impurities such as metals, metal salts containing halogens, acids and alkalis. The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially free (below the detection limit of the measuring device). Is most preferable.
Examples of the method for removing impurities such as metals from various materials include filtration using a filter. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter may be a composite material obtained by combining these materials and ion exchange media. A filter that has been washed in advance with an organic solvent may be used. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different hole diameters and / or materials may be used in combination. Moreover, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.
In addition, as a method of reducing impurities such as metals contained in various materials, an apparatus that selects a raw material having a low metal content as a raw material constituting each material, and performs filter filtration on the raw material constituting each material. Examples thereof include a method of performing distillation under a condition in which the inside is lined with Teflon (registered trademark) and contamination is suppressed as much as possible. The preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.
In addition to filter filtration, impurities may be removed with an adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

<Resin (A)>
The resist composition preferably contains a resin (A). Resin (A) is at least (i) a repeating unit having a group that decomposes by the action of an acid to generate a carboxyl group (may further have a repeating unit having a phenolic hydroxyl group), or at least (ii) It has a repeating unit having a phenolic hydroxyl group.
In addition, when it has the repeating unit which decomposes | disassembles by the effect | action of an acid and has a carboxyl group, the solubility with respect to an alkali developing solution will increase by the effect | action of an acid, and the solubility with respect to an organic solvent will decrease.

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

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

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

The cycloalkyl group represented by R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I) may be monocyclic or polycyclic. Preferable examples include 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.
Examples of the halogen atom of R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.
As the alkyl group contained in the alkoxycarbonyl group of R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I), the same alkyl groups as those described above for R ₄₁ , R ₄₂ and R ₄₃ are preferable.

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

Ar ₄ represents an (n + 1) -valent aromatic ring group. The divalent aromatic ring group in the case where n is 1 may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, and an anthracenylene group, or Examples of preferred aromatic ring groups include heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

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

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

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

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

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

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

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

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

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

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

As the acid eliminable group, there can be, for _{example, -C (R 36) (R} 37) (R 38), - C (R 36) (R 37) (OR 39), - C (R 01) (R 02 ) (OR ₃₉ ) and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R ₀₁ and R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

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

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

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

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

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

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

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

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

The resin (A) preferably further contains a repeating unit having a lactone group.
As the lactone group, any group can be used as long as it contains a lactone structure, but it is preferably a group containing a 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed to form a spiro structure are preferred. It is more preferable to have a repeating unit having a group having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). Further, a group having a lactone structure may be directly bonded to the main chain. Preferred lactone structures are groups represented by general formulas (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14).

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

  Examples of the repeating unit having a group having a lactone structure represented by any of the general formulas (LC1-1) to (LC1-17) include a repeating unit represented by the following general formula (AI). Can do.

In General Formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
Preferable substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom.
Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ is preferably a hydrogen atom or a methyl group.
Ab is a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these. Represent. A linking group represented by a single bond or -Ab ₁ -CO _2- is preferable. Ab ₁ is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.
V represents a group represented by any one of the general formulas (LC1-1) to (LC1-17).

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

  Specific examples of the repeating unit having a group having a lactone structure are given below, but the present invention is not limited thereto.

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

  When the resin (A) has a repeating unit containing an organic group having a polar group, the content thereof is preferably 1 to 30 mol%, more preferably 5 with respect to all repeating units in the resin (A). It is -25 mol%, More preferably, it is 5-20 mol%.

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

R ⁴¹ represents a hydrogen atom or a methyl group. L ⁴¹ represents a single bond or a divalent linking group. L ⁴² represents a divalent linking group. R ⁴⁰ represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.

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

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

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

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

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

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

In the resist composition of the present invention, the content of the resin (A) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass in the total solid content.
In the resist composition of the present invention, the resin (A) may be used alone or in combination.

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

In general formula (VI),
R ₆₁ , R ₆₂ and R ₆₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₆₂ may form a ring with Ar _6, R ₆₂ in this case represents a single bond or an alkylene group.
X ₆ represents a single bond, —COO—, or —CONR ₆₄ —. R ₆₄ represents a hydrogen atom or an alkyl group.
L ₆ represents a single bond or an alkylene group.
Ar ₆ represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when bonded to R ₆₂ to form a ring.
Y ₂ independently represents a hydrogen atom or a group capable of leaving by the action of an acid when n ≧ 2. However, at least one of Y ₂ represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4.
As the group Y ₂ leaving by the action of an acid, a structure represented by the following general formula (VI-A) is more preferable.

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

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

In general formula (3),
Ar ₃ represents an aromatic ring group.
R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, or a heterocyclic group.
M ₃ represents a single bond or a divalent linking group.
Q ₃ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.
Q _3, at least two of _{M 3} and _{R 3} may combine to form a ring.

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

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

  The resin (A) also preferably contains a repeating unit represented by the following general formula (5).

In general formula (5),
R ₄₁ , R ₄₂ and R ₄₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ may be bonded to L ₄ to form a ring, and R ₄₂ in this case represents an alkylene group.
L ₄ represents a single bond or a divalent linking group, and in the case of forming a ring with R ₄₂ , represents a trivalent linking group.
R ₄₄ and R ₄₅ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, or a heterocyclic group.
M ₄ represents a single bond or a divalent linking group.
Q ₄ represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.
At least two of Q ₄ , M ₄ and R ₄₄ may combine to form a ring.
R ₄₁ , R ₄₂ and R ₄₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ may be bonded to L ₄ to form a ring, and R ₄₂ in this case represents an alkylene group.
L ₄ represents a single bond or a divalent linking group, and in the case of forming a ring with R ₄₂ , represents a trivalent linking group.
R ₄₄ and R ₄₅ have the same meaning as R _{3 in} the general formula (3), and the preferred range is also the same.
M ₄ has the same meaning as M _{3 in} the general formula (3), and the preferred range is also the same.
Q ₄ has the same meaning as Q _{3 in} the general formula (3), and the preferred range is also the same. Examples of the ring formed by combining at least two of Q ₄ , M ₄ and R ₄₄ include rings formed by combining at least two of Q ₃ , M ₃ and R ₃ , and the preferred range is the same. It is.

The alkyl group of R _{41 to} R ₄₃ in the general formula (5) is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, which may have a substituent, Examples thereof include alkyl groups having 20 or less carbon atoms such as hexyl group, 2-ethylhexyl group, octyl group and dodecyl group, more preferably alkyl groups having 8 or less carbon atoms, and particularly preferably alkyl groups having 3 or less carbon atoms.
As the alkyl group contained in the alkoxycarbonyl group, the same alkyl groups as those described above for R _{41 to} R ₄₃ are preferable.
The cycloalkyl group may be monocyclic or polycyclic. Preferably, a monocyclic cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent, may be mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.

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

Also when R ₄₂ is to form a is L ₄ and ring an alkylene group, the alkylene group, preferably methylene group, ethylene group, propylene group, butylene group, hexylene group, an alkylene having 1 to 8 carbon atoms such as octylene Groups. An alkylene group having 1 to 4 carbon atoms is more preferable, and an alkylene group having 1 to 2 carbon atoms is particularly preferable. The ring formed by combining R ₄₂ and L ₄ is particularly preferably a 5- or 6-membered ring.

R ₄₁ and R ₄₃ are more preferably a hydrogen atom, an alkyl group, or a halogen atom, a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group (—CH ₂ —OH), A chloromethyl group (—CH ₂ —Cl) and a fluorine atom (—F) are particularly preferred. R ₄₂ is more preferably a hydrogen atom, an alkyl group, a halogen atom, or an alkylene group (forming a ring with L ₄ ), a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group Particularly preferred are (—CH ₂ —OH), a chloromethyl group (—CH ₂ —Cl), a fluorine atom (—F), a methylene group (forms a ring with L ₄ ), and an ethylene group (forms a ring with L ₄ ). .

Examples of the divalent linking group represented by L _4, an alkylene group, a divalent aromatic ring _{group, -COO-L 1 -, -} O-L 1 -, a group formed by combining two or more of these Etc. Here, L ₁ represents an alkylene group, a cycloalkylene group, a divalent aromatic ring group, or a group in which an alkylene group and a divalent aromatic ring group are combined.
L ₄ is preferably a single bond, a group represented by —COO-L ₁ —, or a divalent aromatic ring group. L ₁ is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene or propylene group. As the divalent aromatic ring group, a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, and a 1,4-naphthylene group are preferable, and a 1,4-phenylene group is more preferable.
In the case where L ₄ forms a ring with R _42, examples of the trivalent linking group represented by L _4, from the embodiment described above of the divalent linking group represented by L ₄ 1 single Preferable examples include groups formed by removing any hydrogen atom.

  Although the specific example of the repeating unit represented by General formula (5) below is shown, this invention is not limited to this.

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

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

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

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

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

  Resin (A) may contain the repeating unit represented by the following general formula (V-1) or the following general formula (V-2).

Where
R ₆ and R ₇ are each independently a hydrogen atom, a hydroxy group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group or an acyloxy group, a cyano group, a nitro group, an amino group, A halogen atom, an ester group (-OCOR or -COOR: R represents an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group.
n ₃ represents an integer of 0 to 6.
n ₄ represents an integer of 0-4.
X ⁴ is a methylene group, an oxygen atom or a sulfur atom.
Although the specific example of the repeating unit represented by general formula (V-1) or (V-2) is shown below, it is not limited to these.

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

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

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

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

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

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

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

  Examples of the sulfonylimide anion include saccharin anion.

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

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

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

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

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

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

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

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

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

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

  In addition, examples of the cyclic organic group include a lactone structure, and specific examples thereof include lactone structures represented by the above general formulas (LC1-1) to (LC1-17).

  The cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be linear, branched or cyclic, preferably 1 to 12 carbon atoms), cyclo Alkyl group (which may be monocyclic, polycyclic or spirocyclic, preferably 3 to 20 carbon atoms), aryl group (preferably 6 to 14 carbon atoms), hydroxy group, alkoxy group, ester group, amide Group, urethane group, ureido group, thioether group, sulfonamide group, sulfonic acid ester group and the like. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.

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

In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.

The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ are the same as the aryl group described as the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the aforementioned compound (ZI).
The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may have a substituent. Examples of this substituent include those that the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the above-described compound (ZI) may have.

Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).

In the present invention, the photoacid generator has a volume of 130 to ³ or more by irradiation with an electron beam or extreme ultraviolet rays from the viewpoint of suppressing the diffusion of the acid generated by exposure to the non-exposed portion and improving the resolution. Preferably, the compound generates an acid (more preferably sulfonic acid) having a size of more than 190, more preferably a compound that generates an acid having a volume of 190 to ³ or more (more preferably sulfonic acid). More preferably, the compound generates an acid having a size of 270 以上³ or more (more preferably sulfonic acid), and a compound generating an acid having a volume of 400 体積³ or more (more preferably sulfonic acid). Particularly preferred. However, from the viewpoints of sensitivity and coating solvent solubility, the volume is preferably 2000 ³ or less, and more preferably 1500 ³ or less. The volume value was determined using “WinMOPAC” manufactured by Fujitsu Limited. That is, first, the chemical structure of the acid according to each example is input, and then the most stable conformation of each acid is determined by molecular force field calculation using the MM3 method with this structure as the initial structure, The “accessible volume” of each acid can be calculated by performing molecular orbital calculation using the PM3 method for these most stable conformations.
In the present invention, a photoacid generator that generates an acid upon irradiation with an actinic ray or radiation is exemplified below. In addition, the calculated value of the volume is appended to a part of the example (unit ^{３ 3} ). In addition, the calculated value calculated | required here is a volume value of the acid which the proton couple | bonded with the anion part.
One inch is 1 × 10 ⁻¹⁰ m.

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

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

(C) Solvent The actinic ray-sensitive or radiation-sensitive composition used in the present invention preferably contains a solvent (also referred to as “resist solvent”). This solvent comprises (M1) propylene glycol monoalkyl ether carboxylate and (M2) propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate. It is preferable that at least one of at least one selected from the group is included. In addition, this solvent may further contain components other than component (M1) and (M2).

  The present inventors have found that when such a solvent and the above-described resin are used in combination, the coating property of the composition is improved and a pattern with a small number of development defects can be formed. The reason for this is not necessarily clear, but the present inventors have found that these solvents have a good balance of solubility, boiling point, and viscosity of the resin described above. It is thought that it originates in being able to suppress generation | occurrence | production of a thing.

  As the component (M1), at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate is preferable, and propylene glycol monomethyl ether acetate is particularly preferable.

As the component (M2), the following are preferable.
As propylene glycol monoalkyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferable.
As the lactic acid ester, ethyl lactate, butyl lactate or propyl lactate is preferable.
As the acetate, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate is preferred.
Also preferred is butyl butyrate.
As the alkoxypropionate, methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.
Examples of chain ketones include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, Acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, or methyl amyl ketone are preferred.
As the cyclic ketone, methylcyclohexanone, isophorone, or cyclohexanone is preferable.
As the lactone, γ-butyrolactone is preferable.
As the alkylene carbonate, propylene carbonate is preferable.

  As the component (M2), propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, pentyl acetate, γ-butyrolactone or propylene carbonate is more preferable.

  In addition to the above components, it is preferable to use an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, more preferably 7 to 10) and a hetero atom number of 2 or less.

  Preferred examples of ester solvents having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, and butyl propionate. , Isobutyl isobutyrate, heptyl propionate, butyl butanoate and the like, and it is particularly preferable to use isoamyl acetate.

  As the component (M2), one having a flash point (hereinafter also referred to as fp) of 37 ° C. or higher is preferably used. Examples of such component (M2) include propylene glycol monomethyl ether (fp: 47 ° C.), ethyl lactate (fp: 53 ° C.), ethyl 3-ethoxypropionate (fp: 49 ° C.), methyl amyl ketone (fp: 42 ° C), cyclohexanone (fp: 44 ° C), pentyl acetate (fp: 45 ° C), methyl 2-hydroxyisobutyrate (fp: 45 ° C), γ-butyrolactone (fp: 101 ° C) or propylene carbonate (fp: 132 ° C) ) Is preferred. Of these, propylene glycol monoethyl ether, ethyl lactate, pentyl acetate, or cyclohexanone is more preferred, and propylene glycol monoethyl ether or ethyl lactate is particularly preferred. Here, “flash point” means a value described in a reagent catalog of Tokyo Chemical Industry Co., Ltd. or Sigma Aldrich.

  It is preferable that the solvent contains the component (M1). It is more preferable that the solvent consists essentially of the component (M1) or a mixed solvent of the component (M1) and other components. In the latter case, it is more preferable that the solvent contains both the component (M1) and the component (M2).

  The mass ratio of the component (M1) and the component (M2) is preferably in the range of 100: 0 to 15:85, more preferably in the range of 100: 0 to 40:60, and 100: More preferably, it is in the range of 0 to 60:40. That is, it is preferable that a solvent consists only of a component (M1) or contains both a component (M1) and a component (M2), and those mass ratios are as follows. That is, in the latter case, the mass ratio of the component (M1) to the component (M2) is preferably 15/85 or more, more preferably 40/60 or more, and further preferably 60/40 or more. preferable. Employing such a configuration makes it possible to further reduce the number of development defects.

  In addition, when a solvent contains both a component (M1) and a component (M2), mass ratio of the component (M1) with respect to a component (M2) shall be 99/1 or less, for example.

  As described above, the solvent may further contain components other than the components (M1) and (M2). In this case, the content of components other than the components (M1) and (M2) is preferably in the range of 5% by mass to 30% by mass with respect to the total amount of the solvent.

  The content of the solvent in the actinic ray-sensitive or radiation-sensitive composition is preferably determined so that the solid content concentration of all components is 0.5 to 30% by mass, and is preferably 1 to 20% by mass. More preferably, it is determined. If it carries out like this, the applicability | paintability of actinic-light sensitive or radiation sensitive composition can further be improved.

(E) Basic compound The resist composition of the present invention preferably contains (E) a basic compound in order to reduce a change in performance over time from exposure to heating.
Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The usage-amount of a basic compound is 0.001-10 mass% normally based on solid content of a resist composition, Preferably it is 0.01-5 mass%.

  The use ratio of the acid generator and the basic compound in the composition is preferably acid generator / basic compound (molar ratio) = 2.5 to 300. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid 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, compounds described in paragraphs 0140 to 0144 of JP2013-11833A (amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc.) can be used.

<Hydrophobic resin>
The actinic ray-sensitive or radiation-sensitive composition in the present invention may have a hydrophobic resin different from the resin (A) separately from the resin (A).
The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film. However, unlike a surfactant, it is not always necessary to have a hydrophilic group in the molecule, and polar and / or nonpolar substances can be uniformly distributed. It does not have to contribute to mixing.
Examples of the effect of adding the hydrophobic resin include control of a static or dynamic contact angle on the resist film surface with respect to water, suppression of outgas, and the like.

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

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

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

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

  Regarding the hydrophobic resin, descriptions of <0348> to <0415> of JP2014-010245A can be referred to, and the contents thereof are incorporated in the present specification.

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

In the pattern forming method of the present invention, a resist film can be formed on the substrate using the actinic ray-sensitive or radiation-sensitive composition, and a topcoat layer is formed on the resist film using the topcoat composition. Can do. The thickness of the resist film is preferably 10 to 100 nm, and the thickness of the topcoat layer is preferably 10 to 200 nm, more preferably 20 to 100 nm, and particularly preferably 40 to 80 nm.
As a method of applying the actinic ray-sensitive or radiation-sensitive composition on the substrate, spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.
For example, an actinic ray-sensitive or radiation-sensitive composition is coated on a substrate (eg, silicon / silicon dioxide coating) used for the manufacture of precision integrated circuit elements by an appropriate coating method such as a spinner or a coater, and dried. Then, a resist film is formed. In addition, a known antireflection film can be applied in advance. Further, it is preferable to dry the resist film before forming the top coat layer.
Next, the top coat composition can be applied onto the obtained resist film by the same means as the resist film forming method and dried to form a top coat layer.
The resist film having the top coat layer as an upper layer is usually irradiated with an electron beam (EB), X-rays or EUV light through a mask, preferably baked (heated) and developed. Thereby, a good pattern can be obtained.

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

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

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

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

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

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

The developing solution and the rinsing solution in the present invention can be suitably applied to non-chemical amplification type resist compositions.
As a non-chemical amplification resist composition, for example,
Resist materials whose solubility changes when the main chain is cut by irradiation with g-line, h-line, i-line, KrF, ArF, EB, EUV or the like and the molecular weight is reduced (for example, JP 2013-210411 <0025 >-<0029>, <0056> and US Patent Publications 2015/0008211 <0032>-<0036>, <0063> Copolymers of α-chloroacrylic acid ester compounds and α-methylstyrene compounds Resist materials mainly composed of
Hydrogen silsesquioxane (HSQ) with silanol condensation reaction generated by g-line, h-line, i-line, KrF, ArF, EB or EUV, calixarene substituted with chlorine,
Metal complexes that absorb light such as g-line, h-line, i-line, KrF, ArF, EB or EUV (magnesium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, indium, A complex of tin, antimony, cesium, zirconium, hafnium, etc., including titanium, zirconium and hafnium, which are preferable from the viewpoint of pattern formation), and ligand exchange process in combination with ligand elimination and acid generator (Japanese Patent Application Laid-Open No. 2015-075500 <0017> to <0033>, <0037> to <0047>, Japanese Patent Application Laid-Open No. 2012-185485 <0017> to <0032>, <0043> to <0044>, US Patent Gazette 2012/0208125 <0042> to <0051>, <0066>, etc.).
Further, as the resist composition, the resist compositions described in <0010> to <0062> and <0129> to <0165> described in JP-A-2008-83384 can also be used.

<Container>
An organic solvent (also referred to as “organic processing solution”) that can be used for the developer and the rinsing solution is a container for storing an organic processing solution for patterning a chemically amplified or non-chemically amplified resist film having a storing portion. It is preferable to use a stored one. As this container, for example, the inner wall of the container contacting the organic treatment liquid is a resin different from any of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or rust prevention / metal elution prevention treatment is performed. It is preferably a container for an organic processing liquid for patterning a resist film, which is formed from applied metal. An organic solvent to be used as an organic processing liquid for patterning a resist film is accommodated in the accommodating portion of the accommodating container, and the one discharged from the accommodating portion at the time of patterning the resist film can be used. .

  In the case where the storage container further includes a seal portion for sealing the storage portion, the seal portion is also selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin. It is preferably formed from a resin different from one or more resins, or a metal that has been subjected to a rust prevention / metal elution prevention treatment.

  Here, a seal part means the member which can interrupt | block an accommodating part and external air, and can mention a packing, an O-ring, etc. suitably.

  The resin different from one or more kinds of resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin is preferably a perfluoro resin.

  Examples of perfluororesins include tetrafluoroethylene resin (PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), and tetrafluoride. Ethylene-ethylene copolymer resin (ETFE), ethylene trifluoride-ethylene copolymer resin (ECTFE), vinylidene fluoride resin (PVDF), ethylene trifluoride chloride copolymer resin (PCTFE), vinyl fluoride resin ( PVF) and the like.

  Particularly preferred perfluoro resins include tetrafluoroethylene resin, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene-hexafluoropropylene copolymer resin.

  Examples of the metal in the metal subjected to the rust prevention / metal elution prevention treatment include carbon steel, alloy steel, nickel chromium steel, nickel chromium molybdenum steel, chromium steel, chromium molybdenum steel, manganese steel and the like.

  As the rust prevention / metal elution prevention treatment, it is preferable to apply a film technology.

  There are three types of coating technology: metal coating (various plating), inorganic coating (various chemical conversion treatment, glass, concrete, ceramics, etc.) and organic coating (rust prevention oil, paint, rubber, plastics). .

  Preferable film technology includes surface treatment with a rust preventive oil, a rust preventive agent, a corrosion inhibitor, a chelate compound, a peelable plastic, and a lining agent.

  Among them, various chromates, nitrites, silicates, phosphates, carboxylic acids such as oleic acid, dimer acid, naphthenic acid, carboxylic acid metal soaps, sulfonates, amine salts, esters (glycerin esters of higher fatty acids) And chelating compounds such as ethylene diantetraacetic acid, gluconic acid, nitrilotriacetic acid, hydroxyethyl ethyl orange amine trisuccinic acid, diethylene triamine pentic acid, and fluororesin lining. Particularly preferred are phosphating and fluororesin lining.

  In addition, compared with direct coating treatment, it does not directly prevent rust, but as a treatment method that leads to the extension of the rust prevention period by coating treatment, "pretreatment" is a stage before the rust prevention treatment. It is also preferable to adopt.

  As a specific example of such pretreatment, a treatment for removing various corrosion factors such as chlorides and sulfates existing on the metal surface by washing and polishing can be preferably mentioned.

  Specific examples of the storage container include the following.

・ FluoroPure PFA composite drum manufactured by Entegris (Wetted inner surface; PFA resin lining)
・ JFE steel drums (wetted inner surface; zinc phosphate coating)

  Examples of the storage container that can be used in the present invention include the containers described in JP-A-11-021393 <0013> to <0030> and JP-A-10-45961 <0012> to <0024>. be able to.

  The organic processing liquid of the present invention prevents chemical piping and various parts (filters, O-rings, tubes, etc.) from malfunctioning due to the prevention of static charge and discharge caused by the static charge. Therefore, a conductive compound may be added. Although it does not restrict | limit especially as an electroconductive compound, For example, methanol is mentioned. The addition amount is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less from the viewpoint of maintaining preferable development characteristics. Regarding chemical solution piping members, SUS (stainless steel) or various pipes coated with antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) should be used. it can. Similarly, polyethylene, polypropylene, or fluorine resin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) subjected to antistatic treatment can be used for the filter and O-ring.

In general, the developer and the rinsing liquid are stored in a waste liquid tank through a pipe after use. At that time, if a hydrocarbon-based solvent is used as the rinsing solution, the resist dissolved in the developer is deposited, and in order to prevent the resist from adhering to the back surface of the wafer or the side of the pipe, the solvent in which the resist dissolves is added to the pipe again. There is a way to pass. As a method of passing through the piping, after cleaning with a rinsing liquid, cleaning the back and side surfaces of the substrate with a solvent that dissolves the resist, or passing the solvent through which the resist dissolves without contacting the resist. The method of flowing is mentioned.
The solvent to be passed through the pipe is not particularly limited as long as it can dissolve the resist, and examples thereof include the organic solvents described above, such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl. Ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol 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, or the like can be used. Among these, PGMEA, PGME, and cyclohexanone can be preferably used.

  A semiconductor microcircuit, an imprint mold structure, a photomask, and the like can be manufactured by appropriately performing etching treatment and ion implantation using the pattern obtained by the pattern forming method of the present invention as a mask.

  The pattern formed by the above method can also be used for guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8 Pages 4815-4823). The pattern formed by the above method can be used as a core material (core) of a spacer process disclosed in, for example, Japanese Patent Application Laid-Open Nos. 3-270227 and 2013-164509.

  In addition, about the process in the case of producing the mold for imprinting using the composition of this invention, patent 4109085 gazette, Unexamined-Japanese-Patent No. 2008-162101, and "the foundation of nanoimprint, technical development, and application development, for example" -Nanoimprint substrate technology and latest technology development-edited by Yoshihiko Hirai (Frontier Publishing) ".

  The photomask manufactured using the pattern forming method of the present invention is a light reflective mask used in reflective lithography using EUV light as a light source, even if it is a light transmissive mask used in an ArF excimer laser or the like. May be.

  The present invention also relates to a method for manufacturing an electronic device including the pattern forming method of the present invention described above.

  An electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted on an electric / electronic device (home appliance, OA (Office Appliance) / media-related device, optical device, communication device, etc.). is there.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

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

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

  10 g of the polymer obtained above, 40 mL of methanol, 200 mL of 1-methoxy-2-propanol, and 1.5 mL of concentrated hydrochloric acid were added to the reaction vessel, heated to 80 ° C. and stirred for 5 hours. The reaction solution was allowed to cool to room temperature and dropped into 3 L of distilled water. The filtered solid was dissolved in 200 mL of acetone, dropped again into 3 L of distilled water, and the filtered solid was dried under reduced pressure to obtain Resin (A-1) (8.5 g). The weight average molecular weight by GPC was 10800, and the molecular weight dispersity (Mw / Mn) was 1.55.

Resins (A-2) to (A-4) having the structures shown in Table 1 below were synthesized in the same manner as in Synthesis Example 1 except that the monomers used were changed. The composition ratio (molar ratio) of the resin was calculated by ¹ H-NMR measurement. The weight average molecular weight (Mw: polystyrene conversion) and dispersity (Mw / Mn) of the resin were calculated by GPC (solvent: THF) measurement.

Resins (A-5) to (A-7) having the structures shown in Table 2 below were synthesized in the same manner as in Synthesis Example 1 except that the monomers used were changed. The composition ratio (molar ratio) of the resin was calculated by ¹ H-NMR measurement. The weight average molecular weight (Mw: polystyrene conversion) and dispersity (Mw / Mn) of the resin were calculated by GPC (solvent: THF) measurement.

<Acid generator (B)>
As the acid generator, the following were used.

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

<Solvent (C)>
The following were used as the solvent.
C-1: Propylene glycol monomethyl ether acetate C-2: Propylene glycol C-3: Ethyl lactate C-4: Cyclohexanone

<Resist composition>
Each component shown in the following Table 3 was dissolved in the solvent shown in the same table. The obtained solution was filtered using a polyethylene filter having a pore size of 0.03 μm to obtain a resist composition.

<EUV exposure evaluation>
Using each resist composition shown in Table 3, a resist pattern was formed by the following operation.

[Application of resist composition and baking after application (PB)]
Each resist composition obtained as described above was applied onto a 4-inch silicon wafer subjected to HMDS (hexamethyldisilazane) treatment, baked for 60 seconds under the temperature conditions shown in Table 6, and a film thickness of 40 nm. The resist film was formed.
One inch is 25.4 mm.

〔exposure〕
The wafer on which the resist film was formed was subjected to EUV exposure with dipole illumination at an NA (lens numerical aperture) of 0.3 using an EUV exposure apparatus. Specifically, EUV exposure was performed by changing the exposure amount through a mask including a pattern for forming a 1: 1 line and space pattern having a line width of 20 nm and 45 nm.

[Post-exposure bake (PEB)]
After the exposure, when the wafer was taken out of the EUV exposure apparatus, it was immediately baked for 60 seconds under the temperature conditions shown in Table 6.

〔developing〕
Then, using a shower type developing device (ADE3000S manufactured by ACTES Co., Ltd.), the developer (23 ° C.) described in Table 4 was supplied at a flow rate of 200 mL / min while rotating the wafer at 50 rpm (rpm). Development was performed by spraying for a time.

〔rinse〕
Thereafter, the rinse liquid (23 ° C.) shown in Table 5 was sprayed at a flow rate of 200 mL / min for a predetermined time while rotating the wafer at 50 rotations (rpm) to perform a rinsing process.
Finally, the wafer was dried by rotating at a high speed of 2500 rpm (rpm) for 120 seconds.
The content ratio of the two components of R-5 is a mass ratio.

〔Evaluation test〕
The resist pattern was evaluated for the following items. The results are shown in Table 6.

(Pattern collapse performance)
In the line width of 20 nm, the exposure was performed with irradiation energy that separates and resolves the line to space ratio of 1: 1.
The obtained resist pattern was observed using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.).
The resolution state with a line width of 20 nm obtained by the above method was observed with a scanning electron microscope to determine the number of pattern collapses. 1000 photographs were taken while shifting the observation location by 1 μm, and NG was observed when pattern collapse was observed in one field of view of the photograph, and OK was counted when the pattern was not observed. According to the number of NG, it classified into the following AD. The smaller the NG, the better the pattern collapse performance.
A: 0 B: 1 to 10 C: 11 to 100 D: 101 to 1000

(Bridge performance)
In the line width of 20 nm, the exposure was performed with irradiation energy that separates and resolves the line to space ratio of 1: 1.
The obtained resist pattern was observed using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.).
The resolution of the line width of 20 nm obtained by the above method was observed with a scanning electron microscope to determine the number of bridges. 1000 photographs were taken while shifting the observation location by 1 μm, and NG was observed when the bridge was observed in the field of view of the photograph, and OK was counted when the bridge was not observed. According to the number of NG, it classified into the following AD. The smaller the NG, the better the bridge performance.
A: 0 B: 1 to 10 C: 11 to 100 D: 101 to 1000

(CDU)
The exposure was performed with the irradiation energy for separating and resolving at a line to space ratio of 1: 1 at a line width of 45 nm.
The obtained resist pattern was observed using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.). 100 locations within 150 mm from the center of the wafer were extracted at random, and the pattern line width at that location was measured. The variation of the pattern line width in a total of 100 places was set to 3σ as an index of CDU. A smaller value indicates better performance.

<EB exposure evaluation>
A resist pattern was formed by the following operation using the resist composition described in Table 3 above.

[Application of resist composition and baking after application (PB)]
An organic film forming composition DUV44 (manufactured by Brewer Science) was applied onto a 6-inch silicon wafer, and baked at 200 ° C. for 60 seconds to form an organic film having a thickness of 60 nm. The resist composition described in Table 3 was applied thereon, and baked at the temperature shown in Table 7 for 60 seconds to form a resist film having a thickness of 40 nm.

〔exposure〕
Using the electron beam irradiation apparatus (JBX 6000FS / E manufactured by JEOL Co., Ltd .; acceleration voltage 50 keV) on the wafer on which the resist film is formed, a 1: 1 line AND with a line width of 20 nm to 17.5 nm in increments of 1.25 nm. A space pattern (0.12 mm in the length direction, 20 drawn lines) was exposed by changing the exposure amount.

[Post-exposure bake (PEB)]
After the exposure, when the wafer was taken out from the electron beam irradiation apparatus, it was immediately heated on a hot plate at the temperature shown in Table 7 for 60 seconds.

〔developing〕
Using a shower type developing device (ADE3000S manufactured by ACTES Co., Ltd.), the developer (23 ° C.) described in Table 4 was applied at a flow rate of 200 mL / min for a predetermined time while rotating the wafer at 50 rpm (rpm). Development was performed by spraying.

〔rinse〕
Then, the rinse process (23 degreeC) of the said Table 5 was spray-discharged for a predetermined time by the flow volume of 200 mL / min, rotating the wafer by 50 rotations (rpm), and the rinse process was performed.
Finally, the wafer was dried by rotating at a high speed of 2500 rpm (rpm) for 120 seconds.

  The resist pattern was evaluated by the same method as the “EUV exposure evaluation” described above. The results are shown in Table 7.

  As shown in Tables 6 and 7, regardless of which exposure light source is used, a developer containing an organic solvent having a Hansen solubility parameter δp of 2.9 or more and 5 or less is used as a developer, and a rinse solution It was found that all of the pattern collapse performance, the bridge performance, and the CDU were very good by using a rinse liquid containing an organic solvent containing at least one of a fluorine atom and a silicon atom.

Claims (11)

Resist film formation using an actinic ray-sensitive or radiation-sensitive composition containing a resin whose solubility in an organic solvent is reduced by the action of an acid and a compound that generates acid by actinic rays or radiation. Process,
An exposure step of exposing the resist film;
Developing the exposed resist film with a developer containing 60% by mass or more of an organic solvent having a Hansen solubility parameter δp of 2.9 to 5 with respect to the total mass of the developer;
Rinsing the developed resist film with a rinsing liquid containing 30% by mass or more of an organic solvent (excluding aromatic compounds) containing at least one of fluorine atoms and silicon atoms with respect to the total mass of the rinsing liquid When,
The pattern formation method which has these in order. Resist film formation using an actinic ray-sensitive or radiation-sensitive composition containing a resin whose solubility in an organic solvent is reduced by the action of an acid and a compound that generates acid by actinic rays or radiation. Process,
An exposure step of exposing the resist film;
Developing the exposed resist film using a developer containing an organic solvent having a Hansen solubility parameter δp of 2.9 to 5;
Rinsing the developed resist film with a rinsing liquid containing an organic solvent containing at least one of a fluorine atom and a silicon atom, in this order, and a pattern forming method comprising:
The pattern formation method whose content of the said organic solvent contained in the said rinse liquid is 100 mass% with respect to the total mass of the said rinse liquid. The organic solvent contained in the rinsing liquid contains at least one fluorine atom and a silicon atom, a hydrocarbon solvent or an ether solvent, a pattern forming method according to claim 1 or 2. The organic solvent, containing a fluorine atom, a pattern forming method according to any one of claims 1 to 3 included in the rinsing liquid. The pattern formation method according to claim 4 , wherein the organic solvent contained in the rinse liquid is at least one selected from hydrofluoroether, perfluorocarbon, and hydrofluorocarbon. The organic solvent is at least one selected from perfluorocarbons and hydrofluorocarbons, pattern forming method according to claim 4 or 5 included in the rinsing liquid. The organic solvent contained in the developer, an ester-based solvent, a pattern forming method according to any one of claims 1-6. The organic solvent contained in the developer is an organic solvent having 6 to 10 carbon atoms, a pattern forming method according to any one of claims 1-7. The organic solvent contained in the developer is butyl acetate, pentyl acetate, hexyl acetate, heptyl acetate, isobutyl acetate, isopentyl acetate, isohexyl acetate, secbutyl acetate, tertbutyl acetate, butyl butanoate, 2-ethylhexyl acetate. at least a kind, a pattern forming method according to any one of claims 1-8 selected. The exposure is performed using an electron beam or extreme ultraviolet radiation, the pattern forming method according to any one of claims 1-9. Including a pattern forming method according to any one of claims 1-10, the method of manufacturing an electronic device.