JP2011065105A - Resist pattern forming method and developer used for the method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resist pattern forming method which improves performance in microfabrication of a semiconductor element using a high energy beam, X-ray, electron beam or EUV light and satisfies high sensitivity, high resolution, good line width roughness and process margin at the same time, and a developer used for the method. <P>SOLUTION: The resist pattern forming method includes: a step of forming a resist film using a negative working chemically amplified resist composition which is made negative by a crosslinking reaction; a step of exposing the film; and a step of developing using a developer containing organic solvents after exposure, in this order, wherein the developer contains, as the organic solvents, a solvent (S-1) which serves as a good solvent for the resist film before exposure and a solvent (S-2) which serves as a poor solvent for the resist film before exposure, wherein the boiling point of the solvent (S-2) is higher than that of the solvent (S-1), ((S-2)>(S-1)). The developer used in the method is also provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resist pattern using a negative resist composition that is suitably used for an ultramicrolithography process such as the manufacture of VLSI and high-capacity microchips, an imprint mold structure creation process, and other photofabrication processes. The present invention relates to a forming method. More specifically, the present invention relates to a negative resist composition that can be suitably used for microfabrication of a semiconductor device using electron beams, X-rays, and EUV light (wavelength: around 13 nm) and a resist pattern forming method using the same.

  Conventionally, in the manufacturing process of semiconductor devices such as IC and LSI, fine processing by lithography using a photoresist composition has been performed. In recent years, with the high integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quarter micron region has been required. Along with this, there is a tendency to shorten the exposure wavelength from g-line to i-line, and further to KrF excimer laser light. Furthermore, at present, in addition to excimer laser light, lithography using electron beams, X-rays, or EUV light is being developed. Furthermore, microfabrication by lithography is not limited to the manufacture of semiconductor devices, and application to the production of mold structures (stampers) in so-called nanoimprint technology is also being studied.

These electron beams, X-rays, or EUV light lithography are positioned as next-generation or next-generation pattern forming technologies, and resists with high sensitivity and high resolution are desired.
In particular, high sensitivity is a very important issue for shortening the wafer processing time, but when trying to increase the sensitivity, not only the resolution but also the line width roughness deteriorates. Development of a resist that satisfies the characteristics at the same time is strongly desired.
Here, line width roughness means that when the pattern is viewed from directly above because the resist pattern and the edge of the substrate interface vary irregularly in the direction perpendicular to the line direction due to the characteristics of the resist. Say that the edges look uneven. The unevenness is transferred by an etching process using a resist as a mask, and the electrical characteristics are deteriorated, so that the yield is lowered.

High sensitivity, high resolution, good pattern shape, and good line width roughness are in a trade-off relationship, and it is very important how to satisfy these simultaneously.
The resist composition uses a resin that is insoluble or insoluble in an alkaline developer, and forms a pattern by solubilizing the exposed portion in the alkaline developer by exposure to radiation, There is a “negative type” in which a soluble resin is used and a pattern is formed by making an exposed portion hardly soluble or insoluble in an alkali developer by exposure to radiation.
As a resist suitable for a lithography process using such electron beam, X-ray or EUV light, a chemically amplified positive resist mainly utilizing an acid catalyst reaction has been studied from the viewpoint of high sensitivity, and an alkali as a main component. Chemical amplification type consisting of a phenolic resin (hereinafter abbreviated as phenolic acid-decomposable resin) that is insoluble or sparingly soluble in a developer and soluble in an alkali developer by the action of an acid, and an acid generator Positive resist compositions are effectively used.

On the other hand, there is a demand for forming various patterns such as lines, trenches and holes in the manufacture of semiconductor elements and the like. In order to meet various pattern formation requirements, not only positive type but also negative type resist compositions have been developed (see, for example, Patent Documents 1 and 2).
Patent Document 3 discloses that a resist film made of polymethyl methacrylate or a methyl methacrylate copolymer is developed with CH ₃ COOC _n H _{2n + 1} (n ≦ 4) in place of development with isoamyl acetate in patterning with an electron beam. It is disclosed.
Patent Document 4 discloses that a specific organic solvent such as a benzene-based solvent is used as a developing solution in patterning that uses a polymer chain that is cut by electron beam irradiation to reduce the molecular weight. .
Patent Document 5 discloses that a film containing a halogenated polymer or a polymer having an alkylsiloxy substituent is developed with a critical fluid after exposure in view of environmental problems.
Japanese Patent Application Laid-Open No. H10-228561 uses a positive resist film for development with a mixed solvent of ethyl acetate and isoamyl acetate instead of an alkaline developer.
However, at the same time, we are not satisfied with high sensitivity, high resolution, good process margin (being less susceptible to fluctuations in patterning conditions), and line width roughness reduction in ultra-fine regions. is there.

Japanese Patent Laid-Open No. 2002-148806 JP 2008-268935 A JP-A-62-157539 JP 2006-227174 A Japanese Patent No. 3277114 Japanese Unexamined Patent Publication No. 7-199467

An object of the present invention is to solve the problem of performance improvement technology in microfabrication of a semiconductor element using high energy rays, X-rays, electron beams or EUV light, and has high sensitivity, high resolution, and good line. It is an object of the present invention to provide a resist pattern forming method that satisfies both width roughness and process margin, and a developer used therefor.
In manufacturing a semiconductor element or the like, there is a demand for forming various patterns such as lines, trenches, holes, and the like. Therefore, it is important to satisfy both the process margin, the resolution, the line width roughness, and the sensitivity.

As a result of intensive studies, the present inventors have found that the above object can be achieved by pattern exposure of a chemically amplified crosslinkable negative resist and then developing an unexposed portion using a developer containing an organic solvent. I found it.
That is, the present invention is as follows.

<1> Step (1) of forming a resist film using a negative chemically amplified resist composition, which is negativeized by a crosslinking reaction, step (2) of exposing the film, and using a developer containing an organic solvent after exposure In the method of forming a resist pattern, characterized by having the steps (4) of developing in this order,
The developing solution in step (4) is an organic solvent, a solvent (S-1) that is a good solvent for the resist film before exposure and a solvent (S-2) that is a poor solvent for the resist film before exposure. Contains,
Resist pattern formation characterized by satisfying the relationship of formula (A) where the boiling point of the solvent (S-1) is (bp-1) and the boiling point of the solvent (S-2) is (bp-2) Method.
(Bp-2)> (bp-1) Formula (A)

<2> The resist pattern forming method as described in <1> above, wherein the solvent (S-1) is an ester solvent, a ketone solvent, or an ether solvent.
<3> The resist pattern forming method as described in <1> or <2> above, wherein the solvent (S-2) is a hydrocarbon solvent.
<4> The resist pattern forming method according to any one of <1> to <3>, wherein the solvent (S-2) has a boiling point of 150 ° C. or higher.

<5> The resist pattern forming method according to any one of <1> to <4>, wherein the exposure step (2) is performed with an electron beam or EUV light.
<6> The method for forming a resist pattern according to any one of <1> to <5>, wherein the method is for forming a semiconductor microcircuit.
<7> A negative chemically amplified resist composition that becomes negative by a crosslinking reaction is (A) a resin, (B) a crosslinking agent that crosslinks the resin (A) by the action of an acid, and (C) an actinic ray or radiation. The pattern forming method as described in <1> to <6> above, which comprises a compound that generates an acid upon irradiation of.
<8> The pattern forming method as described in <7> above, wherein the resin (A) is a resin containing a repeating unit represented by the general formula (1).

In formula (1),
A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group.
When a plurality of R ₁ are present, each independently represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group or an alkylcarbonyloxy group.
a represents an integer of 1 to 3.
b represents an integer of 0 to (3-a).
<9> The pattern forming method according to <7> or <8>, wherein the crosslinking agent (B) is a phenol compound.
<10> The pattern forming method as described in <9> above, wherein the crosslinking agent (B) is a phenol compound having two or more benzene rings in the molecule.

<11> The crosslinker (B) is a phenol compound having 2 to 8 crosslinkable groups per molecule that can crosslink the resin (A). Pattern forming method.
<12> The compound (C) is a compound that generates at least one of sulfonic acid, bis (alkylsulfonyl) imide, and tris (alkylsulfonyl) methide by irradiation with actinic rays or radiation. The resist pattern forming method according to any one of <7> to <11> above.
<13> A developer used for the pattern forming method according to any one of <1> to <12>.
<14> A crosslinkable negative chemically amplified resist composition for organic solvent development, which is used in the pattern forming method according to any one of <1> to <12>.

  The present invention provides a pattern forming method using a negative resist composition that can satisfy high sensitivity, high resolution, good pattern shape, good line width roughness, and process margin in an ultrafine region. it can.

Hereinafter, the negative resist composition of the present invention and the pattern forming method using the same will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which 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 addition, “exposure” in the present specification is represented not only by exposure to deep ultraviolet rays, X-rays, EUV light and the like, but also by particle beams such as electron beams and ion beams, unless otherwise specified, such as mercury lamps and excimer lasers. Drawing is also included in the exposure.

[Pattern formation method]
First, the usage form of the negative resist composition of this invention is demonstrated.
The pattern forming method of the present invention includes a step (1) of forming a film using a negative chemically amplified resist composition that is negatively formed by a crosslinking reaction, a step (2) of exposing the film, and an organic solvent after the exposure. It has the process (4) developed using a developing solution in this order.
Here, “negative” means that the molecular weight of the resin increases due to a crosslinking reaction and is insolubilized in a solvent (developer).

(1) Film formation In order to obtain a negative chemically amplified resist composition film, each component described later is dissolved in a solvent, filtered as necessary, and then applied to a support (substrate). The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon having a pore size of 0.1 microns or less, more preferably 0.05 microns or less, and still more preferably 0.03 microns or less.
The composition is applied by a suitable application method such as a spinner onto a substrate (eg, silicon, silicon dioxide coating) used in the manufacture of integrated circuit devices. Thereafter, it is dried to form a photosensitive film.
If necessary, a commercially available inorganic or organic antireflection film can be used. Furthermore, an antireflection film can be applied to the resist lower layer and used.

(2) Exposure The formed film 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 a radiation, For example, they are KrF excimer laser, ArF excimer laser, EUV light, an electron beam, etc., EUV light and an electron beam are preferable.

(3) Baking It is preferable to perform baking (heating) after exposure and before development.
The heating temperature is preferably 80 to 150 ° C, more preferably 90 to 150 ° C, and still more preferably 100 to 140 ° C.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.
Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved.

(4) Development
In the present invention, at least two kinds of organic solvents, that is, a solvent (S-1) that is a good solvent for the resist film before exposure and a solvent (S-2) that is a poor solvent for the resist film before exposure are used. Development is performed using the developer.
・ Developer
The developer used in the present invention includes two types of solvent (S-1) that is a good solvent for the resist film before exposure and a solvent (S-2) that is a poor solvent for the resist film before exposure. And an organic solvent that satisfies the relationship of formula (A) when the boiling point of (S-1) is bp-1 and the boiling point of (S-2) is bp-2.
(Bp-2)> (bp-1) Formula (A)
Here, the good solvent is a solvent having a solubility of 10 nm / second or more, preferably a solubility of 20 nm / second or more, in which the solvent film alone dissolves the resist film before exposure. It is.
The poor solvent is a solvent having a solubility of 0.5 nm / second or less, preferably 0.2 nm / second or less, in which the solvent alone dissolves the resist film before exposure. A solvent, particularly preferably a solvent having a solubility of 0.1 nm / second or less.
The measurement temperature of the dissolution rate is 23 ° C., and examples of the measuring method include the methods in Examples described later.
As represented by the formula (A), a combination organic solvent in which the boiling point (bp-2) of the poor solvent is higher than the boiling point (bp-1) of the good solvent is mixed and used as a developer.
By using such a developer, a good solvent having higher volatility than a poor solvent volatilizes first when the wafer is dried after development. Since the good solvent is less likely to remain in the resist pattern, swelling of the resist pattern, pattern collapse, and the like are improved.

The concentration of the good solvent (S-1) is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more with respect to the total amount of the developer. Since the ratio of the good solvent affects the developability, it is possible to develop in a short time by increasing the good solvent ratio, and it is preferably used from the viewpoint of improving the throughput.
The density | concentration of the solvent (S-2) which is a poor solvent becomes like this. Preferably it is 50 mass% or less with respect to the developing solution whole quantity, More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less.
The total amount of the solvent (S-1) and the solvent (S-2) is preferably 80% by mass or more, more preferably 90% by mass or more, with respect to the total amount of the developer.

The mixing ratio (mass ratio) of the solvent (S-1) and the solvent (S-2) is preferably 1: 0.05 to 1: 1 as solvent (S-1): solvent (S-2). More preferably, it is 1: 0.1 to 1: 0.3.
Further, the developer may be mixed with a solvent other than the above or water within the range having performance. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture. That is, the amount of the organic solvent used in the developer is preferably 90% by mass or more and 99.9999% by mass or less, and preferably 95% by mass or more and 99.999% by mass or less based on the total amount of the developer. More preferred.

The solvent used in the developer, regardless of whether it is a good solvent or a poor solvent, preferably has a boiling point at atmospheric pressure of 100 ° C. or higher, more preferably 110 ° C. or higher, and particularly preferably 120 ° C. or higher. The upper limit is preferably 250 ° C, more preferably 200 ° C. By setting the temperature to 250 ° C. or lower, drying after development is completed in a short time, so that a reduction in throughput can be further suppressed.
By using a solvent having a boiling point of 100 ° C. or higher as a developing solution, evaporation of the developing solution on the substrate or in the developing cup is suppressed, and temperature uniformity in the wafer surface is improved. As a result, in the wafer surface Dimensional uniformity is improved.
In addition, it is preferable that the boiling point of a solvent (S-2) is 150 degreeC or more, and it is more preferable that it is 170 degreeC or more.
When the boiling point of the solvent (S-2) is 150 ° C. or higher, the boiling point of the solvent (S-1) that brings about a preferable boiling point difference in the present invention is lower than 110 ° C., and the dimensional uniformity in the wafer surface is improved.
The difference between the boiling point (bp-1) of the good solvent and the boiling point (bp-2) of the poor solvent [(bp-2)-(bp-1)] is preferably 40 ° C. or higher, more preferably 60 ° C. or higher. By increasing the difference in boiling point, when the wafer is dried, it is difficult for the good solvent to remain, and the above effects are easily exhibited.
As the good solvent, various organic solvents are widely used. For example, solvents such as ester solvents, ketone solvents, alcohol solvents, amide solvents, and ether solvents can be used.
In particular, when a resin containing a repeating unit represented by the formula (1) is used as the component (A), an ester solvent, a ketone solvent, or an ether solvent is preferably selected as a good solvent.

Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate (PGMEA; 1-methoxy-2-acetoxypropane), ethylene glycol monoethyl ether acetate, diethylene glycol mono Butyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, propylene glycol monoethyl ether acetate, propylene glycol diacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate Butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc. Le, ethyl lactate, propylene glycol monomethyl ether acetate is more preferable.
Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, and methyl ethyl ketone. , Methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, etc., and alkyl ketone solvents such as methyl isobutyl ketone, methyl More preferred are amyl ketone, cyclopentanone and cyclohexanone.
Examples of the ether solvent include dioxane, tetrahydrofuran, tetrahydropyran and the like in addition to the glycol ether solvent.
Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, alcohols such as n-octyl alcohol and n-decanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, Glycol solvents such as 1,4-butylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGME; 1-methoxy-2-propano) ), Glycol ether solvents such as ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol, propylene glycol monomethyl ether, phenol solvents such as phenol and cresol, etc. 1-hexanol, 2-hexanol, 1-octanol, 2ethyl-hexanol, propylene glycol monomethyl ether, and cresol are more preferable.
Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.

As the poor solvent, various organic solvents are widely used. For example, solvents such as ester solvents, ketone solvents, alcohol solvents, ether solvents, hydrocarbon solvents and the like can be used.
In particular, when a resin containing a repeating unit represented by the formula (1) is used as the component (A), a hydrocarbon solvent is preferably selected.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as decane, undecane, and dodecane.

  As the good solvent, a developer comprising an organic solvent selected from the group consisting of an ester group having no hydroxyl group in the molecule, a ketone group having no hydroxyl group in the molecule, and an ether group having no hydroxyl group in the molecule is used. It is preferable.

  More specifically, the developer may be a step of performing development using a developer containing an organic solvent that does not contain a hydroxyl group in the molecule, represented by the following general formulas (S1) to (S3). preferable.

In the general formulas (S1) to (S3),
R and R ′ each independently represents an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a cyano group or a halogen atom. Carbon number of an alkyl group, a cycloalkyl group, an alkoxy group, and an alkoxycarbonyl group is the range of 1-6 normally. R and R ′ may be bonded to each other to form a ring. These groups may be further substituted with a hydroxyl group, a carbonyl group, a cyano group, an alkoxy group, an alkyl ester group, or the like.

Examples of the organic solvent having no hydroxyl group in the molecule include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, ethyl-3-ethoxypropionate, propylene glycol diacetate, 3-methoxybutyl acetate, 3-methyl Ester solvents such as -3-methoxybutyl acetate, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, Ketone solvents such as phenylacetone, methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate Dioxane, tetrahydrofuran, preferably ether solvents such as tetrahydro-pyran, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, and more preferably contains at least one member selected from butyl acetate.
Furthermore, you may mix organic solvents other than said good solvent and a poor solvent. In particular, when the polarity difference between the good solvent and the poor solvent is too large, the good solvent and the poor solvent are not mixed alone, so it is preferable to further mix and use a solvent having an intermediate polarity between the good solvent and the poor solvent. .

Surfactant An appropriate amount of a surfactant can be added to the developer containing the organic solvent as necessary.
As the surfactant, the same surfactant as that used in the resist composition described later can be used.
The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

・ Development method As a development method, for example, the substrate is immersed in a tank filled with a developer for a certain period of time (dip method), and the developer is developed on the surface of the substrate by surface tension and kept stationary for a certain period of time. Method (paddle method), Method of spraying developer on substrate surface (spray method), Method of continuing to apply developer while scanning developer application nozzle at constant speed on substrate rotating at constant speed ( Dynamic dispensing method) 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 preferably a time during which the unexposed portion of the resin, the crosslinking agent and the like are sufficiently dissolved, and usually 10 seconds to 300 seconds. More preferably, it is 20 seconds to 120 seconds.
The temperature of the developer is preferably from 0 ° C to 50 ° C, more preferably from 15 ° C to 35 ° C.
The amount of the developer can be appropriately adjusted depending on the developing method.

(5) Rinse In the pattern formation method of this invention, the process (5) wash | cleaned using the rinse liquid containing an organic solvent can also be included after the image development process (4).

-Rinse liquid The organic solvent used in the rinse liquid preferably has a boiling point of 100 ° C or higher at atmospheric pressure, more preferably 110 ° C or higher, and particularly preferably 120 ° C or higher.
By using an organic solvent having a boiling point of 100 ° C. or higher, evaporation of the developer on the substrate or in the developing cup is suppressed, temperature uniformity in the wafer surface is improved, and as a result, the dimensions in the wafer surface are uniform. Sexuality improves.

As the rinse liquid, various organic solvents are used. For example, when the resin containing the repeating unit represented by the formula (1) is used as the component (A), the above-mentioned poor solvent is used. Of these, hydrocarbon solvents are particularly preferred.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as octane, decane, undecane, and dodecane.

  A plurality of these components may be mixed, or may be used by mixing with an organic solvent or water other than those described above.

An appropriate amount of a surfactant can be added to the rinse solution.
As the surfactant, the same surfactant as used in the resist composition described later can be used, and the amount used is usually 0.001 to 5% by mass, preferably based on the total amount of the rinsing liquid. Is 0.005 to 2 mass%, more preferably 0.01 to 0.5 mass%.
The amount of the organic solvent used relative to the rinsing liquid is preferably 90% by mass or more and 99.9999% by mass or less, and more preferably 95% by mass or more and 99.999% by mass or less with respect to the total amount of the rinsing liquid. 97 mass% or more and 99.999 mass% or less is most preferable.

-Rinsing method In the rinsing step, the developed wafer is cleaned using the rinsing liquid containing the organic solvent.
The method of the cleaning treatment is not particularly limited. For example, a method of continuously applying the rinse liquid onto the substrate rotating at a constant speed (rotary coating 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 them, a cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate.
The rinsing time is preferably set so that the developing solvent does not remain on the wafer, and is preferably 10 seconds to 300 seconds. More preferably, it is 20 seconds to 120 seconds.
The temperature of the rinse liquid is preferably 0 ° C. to 50 ° C., more preferably 15 ° C. to 35 ° C.
The amount of rinsing liquid can be appropriately adjusted by a rinsing method.

[Negative chemically amplified resist composition]
Below, the negative chemically amplified resist composition used for the pattern formation method of the present invention, which is negativeized by a crosslinking reaction, will be described.
A negative chemically amplified resist composition that is negatively formed by a crosslinking reaction includes (A) a resin, (B) a crosslinking agent that crosslinks the resin (A) by the action of an acid, (C) an acid upon irradiation with actinic rays or radiation. It is preferable to contain the generated compound.

[1] (A) Resin The resin of component (A) is used together with the compound (B) that crosslinks with an acid. Here, a known resin capable of crosslinking with (B) can be used as the resin of component (A).
The resin (A) preferably has a hydrophilic substituent.
Examples of the hydrophilic substituent include a hydroxyl group, an alkoxyl group, a carboxyl group, an alkoxycarbonyl group, and a carbamoyl group.
For example, hydroxystyrene, partially hydrogenated hydroxystyrene, novolak resin, (meth) acrylic polymer (such as (meth) acrylic acid-containing polymer), hydroxyl group-containing polymer, polyvinyl acetate, diene copolymer, epoxy group-containing polymer are preferable. It can mention as resin of the (A) component which can be used.
From the viewpoint of secondary electron generation efficiency in electron beam and EUV exposure, the resin of component (A) preferably has a benzene ring, such as styrene resin and novolak resin, and is represented by the general formula (1). More preferably, it contains a repeating unit.

In formula (1),
A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group.
When a plurality of R's are present, each independently represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group or an alkylcarbonyloxy group.
a represents an integer of 1 to 3. Preferably a is 1.
b represents an integer of 0 to (3-a). b is preferably 0 or 1, more preferably 0.

In general formula (1), the alkyl group as A may further have a substituent, and an alkyl group having 1 to 3 carbon atoms is preferable. The cycloalkyl group as A may further have a substituent and may be monocyclic or polycyclic. Examples of the halogen atom as A include Cl, Br, and F. A is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (such as a methyl group or an ethyl group), and particularly preferably a hydrogen atom or a methyl group.
Examples of R include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, and an alkylsulfonyloxy group, and may further have a substituent. Examples of the halogen atom as R include Cl, Br, F, and I. Moreover, when it has several R, they may mutually form a ring.

  R is preferably a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 1 to 8 carbon atoms which may have a substituent, or a substituent. A cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 15 carbon atoms which may have a substituent, and a 7 to 16 carbon atom which may have a substituent. They are an aralkyl group, an optionally substituted alkoxy group having 1 to 8 carbon atoms, or an optionally substituted alkylcarbonyloxy group having 1 to 8 carbon atoms.

  As R, more preferably, each independently, a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkyl group having 1 to 4 carbon atoms which may have a substituent. An alkoxy group, an alkylcarbonyloxy group having 1 to 4 carbon atoms which may have a substituent, particularly preferably a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 3 carbon atoms ( Methyl group, ethyl group, propyl group, isopropyl group) and an alkoxy group having 1 to 3 carbon atoms (methoxy group, ethoxy group, propyloxy group, isopropyloxy group).

  Examples of the substituent that A and R may further have include an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, etc.), aryl group (phenyl). Group, naphthyl group, etc.), aralkyl group, hydroxyl group, alkoxy group (methoxy group, ethoxy group, butoxy group, octyloxy group, dodecyloxy group, etc.), acyl group (acetyl group, propanoyl group, benzoyl group, etc.), oxo A group having 15 or less carbon atoms is preferable.

  The substituents (— (OH) a and (R) b) in the repeating unit represented by the general formula (1) are any of the para position, the meta position, and the ortho position with respect to the bond from the main chain of the resin. However, it is preferable that —OH is present at least in the meta position.

  The resin of the component (A) used in the present invention may have at least one repeating unit represented by the general formulas (2) to (4) together with the repeating unit represented by the general formula (1).

In general formulas (2) to (4),
A has the same meaning as A in formula (1).
X represents a single bond, —COO— group, —O— group, —CON (R ₁₆ ) — group, and R ₁₆ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (methyl group, ethyl group, propyl group, etc.) ). X is preferably a single bond, —COO—, or —CON (R ₁₆ ) —, and particularly preferably a single bond or a —COO— group.
The ring structure represented by Y represents a polycyclic aromatic hydrocarbon ring structure having three or more rings, and preferably represents any of the following structural formulas.

R _{11 to} R ₁₅ each independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, or an alkylcarbonyloxy group. Specific examples of these groups include the same groups as R in the general formula (1).
R _{101 to} R ₁₀₆ are each independently a hydroxy group, a halogen atom (Cl, Br, F, I), an optionally substituted linear or branched alkyl group having 1 to 8 carbon atoms, a substituted group A linear or branched alkoxy group having 1 to 8 carbon atoms which may have a group, a linear or branched alkylcarbonyloxy group having 1 to 8 carbon atoms which may have a substituent, and a substituent A linear or branched alkylsulfonyloxy group having 1 to 8 carbon atoms which may have a group, an alkenyl group having 1 to 8 carbon atoms which may have a substituent, and a substituent. An aryl group having 7 to 15 carbon atoms, an aralkyl group having 7 to 16 carbon atoms which may have a substituent, a carboxy group, and a perfluoroalkyl group having 1 to 4 carbon atoms which may have a hydroxyl group. Represents.
c to h each independently represents an integer of 0 to 3.

Examples of these substituents include the same ones as mentioned as examples of the substituent for R in the general formula (1).
Preferably, each of R _{101 to} R ₁₀₆ is independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an optionally substituted carbon atom having 1 to 1 carbon atoms. An alkoxy group having 4 alkoxy groups and an alkylcarbonyloxy group having 1 to 4 carbon atoms which may have a substituent, particularly preferably a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 1 to 3 carbon atoms. Group (methyl group, ethyl group, propyl group, isopropyl group), C1-C3 alkoxy group (methoxy group, ethoxy group, propyloxy group, isopropyloxy group), C1-C3 alkylcarbonyloxy group ( Acetyl group, propionyl group, etc.).

The resin of the component (A) used in the present invention is a resin having only one type of repeating unit represented by the general formula (1), a resin having two or more types of repeating units represented by the general formula (1), Any of resins having at least one of the repeating units represented by the general formula (1) and the repeating units represented by the general formulas (2) to (4) may be used. Other polymerizable monomers that can control the property may be polymerized.
Examples of these polymerizable monomers include styrene, alkyl-substituted styrene, alkoxy-substituted styrene, O-alkylated styrene, O-acylated styrene, hydrogenated hydroxystyrene, maleic anhydride, acrylic acid derivatives (acrylic acid, acrylic acid Esters), methacrylic acid derivatives (methacrylic acid, methacrylic esters, etc.), N-substituted maleimides, acrylonitrile, methacrylonitrile, and the like, but are not limited thereto.
In addition to the above, as a preferable repeating unit of the resin, a unit having a cyclic structure in the main chain (such as a unit derived from a monomer having an indene structure), a unit having a naphthol structure, a —C (CF 3) ₂ OH group Examples thereof include repeating units.

The range of the content of the repeating unit represented by the general formula (1) in the resin of the component (A) used in the present invention is generally 50 to 100 mol%, preferably 70 to 100 mol%.
In the resin of component (A), the ratio of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formulas (2) to (4) is 100/0 to 50/50 in molar ratio. Is more preferable, 100/0 to 60/40 is more preferable, and 100/0 to 70/30 is particularly preferable.
(A) The preferable molecular weight of resin of a component is 1000-50000 as a mass mean molecular weight, More preferably, it is 2000-20000.
(A) The preferable molecular weight distribution (Mw / Mn) of resin of a component is 1.0-2.0, More preferably, it is 1.0-1.35.
The amount of the component (A) resin added is generally 30 to 95% by mass, preferably 40 to 90% by mass, particularly preferably 50 to 80% by mass, based on the total solid content of the composition. In addition, the molecular weight and molecular weight distribution of resin are defined as a polystyrene conversion value by GPC measurement.

  The resin of component (A) can be synthesized by a known radical polymerization method or anionic polymerization method. For example, in the radical polymerization method, a vinyl monomer is dissolved in a suitable organic solvent, and a peroxide (benzoyl peroxide, etc.), a nitrile compound (azobisisobutyronitrile, etc.), or a redox compound (cumene hydroperoxide-first A polymer can be obtained by reacting at a room temperature or under a heating condition using an iron salt or the like) as an initiator. In the anionic polymerization method, a vinyl monomer can be dissolved in a suitable organic solvent, and a polymer can be obtained usually by reacting under a cooling condition using a metal compound (such as butyl lithium) as an initiator.

Although the specific example of resin of the (A) component used by this invention below is shown, this invention is not limited to these.
In the specific examples, n represents a positive integer.
x, y, z represents the molar ratio of the resin composition, and in the case of a resin composed of two components, x = 10 to 95, y = 5 to 90, preferably x = 40 to 90, y = 10 to 60 Is done. In the resin composed of three components, x = 10 to 90, y = 5 to 85, z = 5 to 85, preferably x = 40 to 80, y = 10 to 50, z = 10 to 50 are used. . Moreover, these may be used independently and may mix and use 2 or more types.

[2] (B) Crosslinking agent In the present invention, a compound that crosslinks the resin (A) by the action of an acid (hereinafter referred to as a crosslinking agent) is used together with the (A) resin. Here, a known crosslinking agent can be used effectively.
The crosslinking agent (B) is, for example, a compound or resin having a crosslinkable group capable of crosslinking the resin (A). Preferably, the crosslinkable group includes a hydroxymethyl group, an alkoxymethyl group, an acyloxymethyl group, Alternatively, it is a compound or resin having two or more alkoxymethyl ether groups, or an epoxy compound.
More preferably, alkoxymethylated, acyloxymethylated melamine compounds or resins, alkoxymethylated, acyloxymethylated urea compounds or resins, hydroxymethylated or alkoxymethylated phenolic compounds or resins, and alkoxymethyletherified phenolic compounds or resins, etc. Is mentioned.

As the particularly preferred component (B), the molecular weight is 1200 or less, the molecule contains 3 to 5 benzene rings, and further has two or more hydroxymethyl groups or alkoxymethyl groups. Mention may be made of phenol derivatives formed by concentrating the groups on at least one of the benzene rings, or by linking them together. By using such a phenol derivative, the effect of the present invention can be made more remarkable. As the alkoxymethyl group bonded to the benzene ring, those having 6 or less carbon atoms are preferable. Specifically, a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an i-propoxymethyl group, an n-butoxymethyl group, an i-butoxymethyl group, a sec-butoxymethyl group, and a t-butoxymethyl group are preferable. Furthermore, alkoxy-substituted alkoxy groups such as 2-methoxyethoxy group and 2-methoxy-1-propyl group are also preferable.
The crosslinking agent (B) is preferably a phenol compound having a benzene ring in the molecule, more preferably a phenol compound having two or more benzene rings in the molecule, and a phenol compound containing no nitrogen atom. It is preferable that
The cross-linking agent (B) is preferably a phenol compound having 2 to 8 crosslinkable groups per molecule that can crosslink the resin (A), and more preferably 3 to 6 crosslinkable groups.

Among these phenol derivatives, particularly preferable ones are listed below. In the formula, L ^{1 to} L ⁸ represent a crosslinkable group and may be the same or different, and the crosslinkable group preferably represents a hydroxymethyl group, a methoxymethyl group or an ethoxymethyl group.

What is marketed can also be used for a crosslinking agent (B), and it can also synthesize | combine by a well-known method. For example, a phenol derivative having a hydroxymethyl group is obtained by reacting a phenol compound not having a corresponding hydroxymethyl group (a compound in which L ^{1 to} L ⁸ are hydrogen atoms in the above formula) with formaldehyde in the presence of a base catalyst. be able to.
At this time, in order to prevent resinification or gelation, the reaction temperature is preferably 60 ° C. or lower. Specifically, it can be synthesized by the methods described in JP-A-6-282067, JP-A-7-64285 and the like.

  A phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst. At this time, in order to prevent resinification and gelation, the reaction temperature is preferably 100 ° C. or lower. Specifically, it can be synthesized by the method described in EP632003A1 and the like. A phenol derivative having a hydroxymethyl group or an alkoxymethyl group synthesized in this manner is preferable from the viewpoint of stability during storage, but a phenol derivative having an alkoxymethyl group is particularly preferable from the viewpoint of stability during storage. Such a phenol derivative having two or more hydroxymethyl groups or alkoxymethyl groups in total and concentrated on any benzene ring or distributed and bonded may be used alone or in combination of two kinds. A combination of the above may also be used.

  Examples of the crosslinking agent also include the following (i) a compound having an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-acyloxymethyl group, and (ii) an epoxy compound.

  (I) The compound having an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-acyloxymethyl group has two or more partial structures represented by the following general formula (CLNM-1) (more preferably 2 ~ 8) are preferred.

In the general formula (CLNM-1),
R ^NM1 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an oxoalkyl group.

In general formula (CLNM-1), the alkyl group of R ^NM1 is preferably a linear or branched alkyl group having 1 to 6 carbon atoms. The cycloalkyl group of R ^NM1 is preferably a cycloalkyl group having 5 to 6 carbon atoms. The oxoalkyl group of R ^NM1 is preferably an oxoalkyl group having 3 to 6 carbon atoms, and examples thereof include a β-oxopropyl group, a β-oxobutyl group, a β-oxopentyl group, and a β-oxohexyl group. it can.

  As a more preferable embodiment of the compound having two or more partial structures represented by the general formula (CLNM-1), the following general formula (CLNM-) having two or more partial structures represented by the general formula (CLNM-1) is preferable. 2) a urea-based crosslinking agent represented by the following general formula (CLNM-3), an alkylene urea-based crosslinking agent represented by the following general formula (CLNM-4), or a glycoluril-based crosslinking agent represented by the following general formula (CLNM-4) A melamine-based crosslinking agent represented by the formula (CLNM-5) can be given.

In the general formula (CLNM-2),
, Each R ^NM1 independently, are those in formula (CLNM-1) ^at, the same as ^{R NM1.}
R ^NM2 each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 6 carbon atoms), or a cycloalkyl group (preferably having 5 to 6 carbon atoms).

  Specific examples of the urea crosslinking agent represented by the general formula (CLNM-2) include, for example, N, N-di (methoxymethyl) urea, N, N-di (ethoxymethyl) urea, N, N-di (Propoxymethyl) urea, N, N-di (isopropoxymethyl) urea, N, N-di (butoxymethyl) urea, N, N-di (t-butoxymethyl) urea, N, N-di (cyclohexyloxy) And methyl) urea, N, N-di (cyclopentyloxymethyl) urea, N, N-di (adamantyloxymethyl) urea, N, N-di (norbornyloxymethyl) urea and the like.

In the general formula (CLNM-3),
, Each R ^NM1 independently, are those in formula (CLNM-1) ^at, the same as ^{R NM1.}
R ^NM3 each independently represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group (preferably having 1 to 6 carbon atoms), a cycloalkyl group (preferably having 5 to 6 carbon atoms), an oxoalkyl group (having a carbon number). 3-6 are preferable), an alkoxy group (preferably having 1 to 6 carbon atoms) or an oxoalkoxy group (preferably having 2 to 6 carbon atoms) is represented.
G represents a single bond, an oxygen atom, a sulfur atom, an alkylene group (preferably having 1 to 3 carbon atoms) or a carbonyl group. More specifically, a methylene group, ethylene group, propylene group, 1-methylethylene group, hydroxymethylene group, cyanomethylene group and the like can be mentioned.

  Specific examples of the alkylene urea crosslinking agent represented by the general formula (CLNM-3) include, for example, N, N-di (methoxymethyl) -4,5-di (methoxymethyl) ethylene urea, N, N- Di (ethoxymethyl) -4,5-di (ethoxymethyl) ethyleneurea, N, N-di (propoxymethyl) -4,5-di (propoxymethyl) ethyleneurea, N, N-di (isopropoxymethyl) -4,5-di (isopropoxymethyl) ethyleneurea, N, N-di (butoxymethyl) -4,5-di (butoxymethyl) ethyleneurea, N, N-di (t-butoxymethyl) -4 5-di (t-butoxymethyl) ethyleneurea, N, N-di (cyclohexyloxymethyl) -4,5-di (cyclohexyloxymethyl) ethyleneurea, N, N-di (cyclo Nthyloxymethyl) -4,5-di (cyclopentyloxymethyl) ethyleneurea, N, N-di (adamantyloxymethyl) -4,5-di (adamantyloxymethyl) ethyleneurea, N, N-di (nor Bornyloxymethyl) -4,5-di (norbornyloxymethyl) ethyleneurea and the like.

In the general formula (CLNM-4),
, Each R ^NM1 independently, are those in formula (CLNM-1) ^at, the same as ^{R NM1.}
R ^NM4 each independently represents a hydrogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group or an alkoxy group.

R ^NM4 alkyl group (preferably having 1 to 6 carbon atoms), cycloalkyl group (preferably having 5 to 6 carbon atoms), alkoxy group (preferably having 1 to 6 carbon atoms), more specifically, methyl group, Examples include an ethyl group, a butyl group, a cyclopentyl group, a cyclohexyl group, a methoxy group, an ethoxy group, and a butoxy group.

  Specific examples of the glycoluril-based crosslinking agent represented by the general formula (CLNM-4) include, for example, N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N, N-tetra ( Ethoxymethyl) glycoluril, N, N, N, N-tetra (propoxymethyl) glycoluril, N, N, N, N-tetra (isopropoxymethyl) glycoluril, N, N, N, N-tetra (butoxy) Methyl) glycoluril, N, N, N, N-tetra (t-butoxymethyl) glycoluril, N, N, N, N-tetra (cyclohexyloxymethyl) glycoluril, N, N, N, N-tetra ( Cyclopentyloxymethyl) glycoluril, N, N, N, N-tetra (adamantyloxymethyl) glycoluril, N, N, N, N- Tiger (norbornyloxymethyl) glycoluril, and the like.

In the general formula (CLNM-5),
, Each R ^NM1 independently, are those in formula (CLNM-1) ^at, the same as ^{R NM1.}
R ^NM5 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an atomic group represented by the following general formula (CLNM-5 ′).
R ^NM6 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an atomic group represented by the following general formula (CLNM-5 ″).

In the general formula (CLNM-5 ′),
R ^NM1 are those in formula (CLNM-1) ^at, the same as ^{R NM1.}
In the general formula (CLNM-5 ″),
R ^NM1 of the general formula are those (CLNM-1) in ^at, the same as ^{R NM1, R NM5} are those formula (CLNM-5) in the same manner as in ^{R NM5.}

Alkyl group R ^NM5 and ^{R NM6} (1 to 6 carbon atoms is preferred), cycloalkyl groups (5 to 6 carbon atoms is preferred), an aryl group (having 6 to 10 carbon atoms is preferred), and more specifically, Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a phenyl group, and a naphthyl group.

  Examples of the melamine crosslinking agent represented by the general formula (CLNM-5) include N, N, N, N, N, N-hexa (methoxymethyl) melamine, N, N, N, N, N, N Hexa (ethoxymethyl) melamine, N, N, N, N, N, N-hexa (propoxymethyl) melamine, N, N, N, N, N, N-hexa (isopropoxymethyl) melamine, N, N , N, N, N, N-hexa (butoxymethyl) melamine, N, N, N, N, N, N-hexa (t-butoxymethyl) melamine, N, N, N, N, N, N-hexa (Cyclohexyloxymethyl) melamine, N, N, N, N, N, N-hexa (cyclopentyloxymethyl) melamine, N, N, N, N, N, N-hexa (adamantyloxymethyl) melamine, N, N , N, N, N, N-hexa ( Rubornyloxymethyl) melamine, N, N, N, N, N, N-hexa (methoxymethyl) acetoguanamine, N, N, N, N, N, N-hexa (ethoxymethyl) acetoguanamine, N, N, N, N, N, N-hexa (propoxymethyl) acetoguanamine, N, N, N, N, N, N-hexa (isopropoxymethyl) acetoguanamine, N, N, N, N, N, N -Hexa (butoxymethyl) acetoguanamine, N, N, N, N, N, N-hexa (t-butoxymethyl) acetoguanamine, N, N, N, N, N, N-hexa (methoxymethyl) benzoguanamine, N, N, N, N, N, N-hexa (ethoxymethyl) benzoguanamine, N, N, N, N, N, N-hexa (propoxymethyl) benzoguanamine, N, N, N, N, N, N Hexa (isopropoxymethyl) benzoguanamine, N, N, N, N, N, N-hexa (butoxymethyl) benzoguanamine, N, N, N, N, N, N-hexa (t-butoxymethyl) benzoguanamine, etc. Can be mentioned.

The groups represented by R ^{NM1 to} R ^NM6 in the general formulas (CLNM-1) to (CLNM-5) may further have a substituent. Examples of the substituent that R ^{NM1 to} R ^NM6 may have include, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a cycloalkyl group (preferably having 3 to 20 carbon atoms), and an aryl group (preferably 6 to 14 carbon atoms), alkoxy group (preferably 1 to 20 carbon atoms), cycloalkoxy group (preferably 3 to 20 carbon atoms), acyl group (preferably 2 to 20 carbon atoms), acyloxy group (preferably carbon 2-20) etc. can be mentioned.

  (Ii) As an epoxy compound, the compound represented by the following general formula (EP2) is mentioned.

In formula (EP2),
R ^{EP1 to} R ^EP3 each independently represent a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group, and the alkyl group and the cycloalkyl group may have a substituent. R ^EP1 and R ^EP2 , R ^EP2 and R ^EP3 may be bonded to each other to form a ring structure.
Examples of the substituent that the alkyl group and cycloalkyl group may have include a hydroxyl group, a cyano group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkylthio group, an alkylsulfone group, and an alkylsulfonyl group. Groups, alkylamino groups, alkylamide groups, and the like.
^QEP represents a single bond or an ^nEP- valent organic group. R ^EP1 to R ^EP3 may be combined to form a ring structure with ^{Q EP} not only with each other but.
n ^EP represents an integer of 2 or more, preferably 2 to 10, more preferably 2 to 6. However, ^nEP is 2 when ^QEP is a single bond.

When ^QEP is an ^nEP- valent organic group, a chain or cyclic saturated hydrocarbon structure (preferably having 2 to 20 carbon atoms) or an aromatic ring structure (preferably having 6 to 30 carbon atoms), or these are ethers and esters , Amides, sulfonamides and the like linked structures are preferred.

  Specific examples of the compound (B) having an epoxy structure are illustrated below, but the present invention is not limited thereto.

The cross-linking agent prevents the remaining film ratio and the resolution from decreasing, and from the viewpoint of maintaining good stability during storage of the resist solution, preferably 3 to 65% by mass in the total solid content of the resist composition, More preferably, it is used in an added amount of 5 to 50% by mass, and more preferably 10 to 45% by mass.
In this invention, a crosslinking agent may be used independently and may be used in combination of 2 or more type. For example, in addition to the above-mentioned phenol derivative, when other cross-linking agents such as the above (i), (ii) and the like are used in combination, the ratio of the above-mentioned phenol derivative and other cross-linking agent is 100/0 in molar ratio. 20/80, preferably 90/10 to 40/60, more preferably 80/20 to 50/50.

[3] (C) Compound that generates acid upon irradiation with actinic ray or radiation The composition of the present invention contains a compound that generates acid upon irradiation with actinic ray or radiation (hereinafter also referred to as “acid generator”). To do.
The acid generator is not particularly limited as long as it is a known acid generator, but is a compound that generates at least one of sulfonic acid, bis (alkylsulfonyl) imide, or tris (alkylsulfonyl) methide upon irradiation with actinic rays or radiation. Is preferred.
More preferred examples include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).

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

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

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

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

  The alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7), an alkylthio group (preferably 1 to 15 carbon atoms), an alkylsulfonyl group (preferably 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably 2 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 6 to 12 carbon atoms, such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group, and the like.

  Examples of the sulfonylimide anion include saccharin anion.

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

  Examples of other non-nucleophilic anions include fluorinated phosphorus, fluorinated boron, and fluorinated antimony.

  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, an alkyl group, or a group selected from an alkyl group substituted with at least one fluorine atom, and R ¹ and R ² in the case where a plurality of R ¹ and R ^{2 are present.} May be the same or different.
L represents a single bond or a divalent linking group, and when there are a plurality of L, they may be the same or different.
A represents a group having a cyclic structure.
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. Specifically, a fluorine _{atom, CF 3, C 2 F 5} , C 3 F 7, C 4 F 9, CH 2 CF 3, CH 2 CH 2 CF 3, CH 2 C 2 F 5, CH 2 CH 2 C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F ₉ are mentioned, among which a fluorine atom and CF ₃ are preferable.

The alkyl group in R ¹ and R ^{2 and} the alkyl group substituted with at least one fluorine atom are preferably those having 1 to 4 carbon atoms.
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, Examples include alkenylene groups. Of these, —COO—, —OCO—, —CO—, and —O— are preferable, and —COO— and —OCO— are more preferable.

The group having a cyclic structure of A is not particularly limited as long as it has a cyclic structure. The group having an alicyclic group, an aryl group, or a heterocyclic structure (not only those having an aromatic attribute, but also having an aromatic attribute). 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 group having a heterocyclic structure include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, a furan ring, a thiophene ring, and a pyridine ring are preferable.
The group having the cyclic structure may have a substituent, and the substituent may be an alkyl group (which may be linear, branched or cyclic, preferably having 1 to 12 carbon atoms), Examples include aryl groups (preferably having 6 to 14 carbon atoms), hydroxy groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamido groups, sulfonic acid ester groups, and the like.

_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. These aryl groups may further have a substituent. Examples of the substituent include halogen atoms such as nitro groups and fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), 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) and the like, but are not limited thereto.

In _the case of forming the two members ring structure of R 201 _{to R 203,} it is preferably a structure represented by the following general formula (A1).

In general formula (A1),
R ^{1a to} R ^13a each independently represents a hydrogen atom or a substituent.
It is preferable that 1-3 are not a hydrogen atom among R ^{< 1a} > -R < ^13a >, and it is more preferable that any one of R ^{< 9a} > -R < ^13a > is not a hydrogen atom.
Za is a single bond or a divalent linking group.
X ⁻ has the same meaning as Z ⁻ in formula (ZI).

Specific examples when R ^{1a to} R ^13a are not a hydrogen atom include a halogen atom, a linear, branched, cyclic alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, nitro group, carboxyl group , Alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, amino Carbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl And arylsulfinyl groups, alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl and heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphini Ruamino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (—B (OH) ₂ ), phosphato group (—OPO (OH) ₂ ), sulfato group (—OSO ₃ H), other Known substituents are listed as examples.
As a case where R ^{1a to} R ^13a are not a hydrogen atom, a linear, branched or cyclic alkyl group substituted with a hydroxyl group is preferable.

  Examples of the divalent linking group for Za include an alkylene group, an arylene group, a carbonyl group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamide group, an ether group, a thioether group, an amino group, a disulfide group, an acyl group, and an alkyl group. A sulfonyl group, -CH = CH-, an aminocarbonylamino group, an aminosulfonylamino group, etc. are mentioned.

In addition, as a preferable structure when at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group, paragraphs 0047 and 0048 of JP-A No. 2004-233661, paragraphs 0040 to of JP-A No. 2003-35948 Compounds exemplified as formulas (I-1) to (I-70) in U.S. Patent Application Publication No. 2003 / 0224288A1, and formula (IA-1) in U.S. Patent Application Publication No. 2003 / 0077540A1. ) To (IA-54) and cation structures such as compounds exemplified as formulas (IB-1) to (IB-24).

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-1). is there.
The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may have a substituent. Even the substituent, an aryl group of _R 201 _{to R 203} in the compound of the aforementioned (ZI-1), alkyl groups include those which may have a cycloalkyl group.

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

  Examples of the acid generator further include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.

  Among acid generators, particularly preferred examples are given below.

An acid generator can be used individually by 1 type or in combination of 2 or more types. When two or more types are used in combination, for example, (1) when two types of PAGs having different acid strengths are used in combination, (2) two types of acid generators having different sizes (molecular weight or carbon number) of the generated acid are used in combination. In some cases, such an embodiment is preferable.
As an aspect of (1), for example, combined use of a sulfonic acid generator having fluorine and a tris (fluoroalkylsulfonyl) methide acid generator, a combined use of a sulfonic acid generator having fluorine and a sulfonic acid generator having no fluorine Further, the combined use of an alkyl sulfonic acid generator and an aryl sulfonic acid generator is conceivable.
As an aspect of (2), for example, a combination of two acid generators in which the number of carbon atoms of the generated acid anion is 4 or more can be considered.
The content of the acid generator in the composition (the total amount when a plurality of acid generators are used in combination) is preferably 0.1 to 30% by mass, more preferably 0.5 to 20 based on the total solid content of the composition. % By mass, more preferably 1 to 15% by mass.

[4] Basic compound The resist composition of the present invention preferably contains a basic compound.
The basic compound is preferably a nitrogen-containing organic basic compound.
Although the compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(4) is used preferably.

(1) Compound represented by the following general formula (BS-1)

In general formula (BS-1),
R _bs1 independently represents any of a hydrogen atom, an alkyl group (straight or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group, and an aralkyl group. However, not all three Rs are hydrogen atoms.
Although carbon number of the alkyl group as _Rbs1 is not specifically limited, Usually, 1-20, Preferably it is 1-12.
Although carbon number of the cycloalkyl group as _Rbs1 is not specifically limited, Usually, 3-20, Preferably it is 5-15.
Although carbon number of the aryl group as _Rbs1 is not specifically limited, Usually, 6-20, Preferably it is 6-10. Specific examples include a phenyl group and a naphthyl group.
Although carbon number of the aralkyl group as _Rbs1 is not specifically limited, Usually, 7-20, Preferably it is 7-11. Specific examples include a benzyl group.
In the alkyl group, cycloalkyl group, aryl group or aralkyl group as R _bs1 , a hydrogen atom may be substituted with a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, and an alkyloxycarbonyl group.
In the compound represented by the general formula (BS-1), it is preferable that only one of three Rs is a hydrogen atom, or all Rs are not hydrogen atoms.

Specific examples of the compound of the general formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexylmethylamine, Tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N, N- Examples include dihexylaniline.
In addition, a compound in which at least one R in the general formula (BS-1) is an alkyl group substituted with a hydroxyl group can be mentioned as one of preferable embodiments. Specific examples of the compound include triethanolamine and N, N-dihydroxyethylaniline.

Moreover, the alkyl group as _Rbs1 may have an oxygen atom in the alkyl chain, and an oxyalkylene chain may be formed. As the oxyalkylene chain, —CH ₂ CH ₂ O— is preferable.
Specific examples include tris (methoxyethoxyethyl) amine and compounds exemplified in column 3, line 60 and thereafter of US Pat. No. 6,040,112.

(2) Compound having a nitrogen-containing heterocyclic structure The heterocyclic structure may or may not have aromaticity. Moreover, you may have two or more nitrogen atoms, Furthermore, you may contain hetero atoms other than nitrogen. Specifically, compounds having an imidazole structure (2-phenylbenzimidazole, 2,4,5-triphenylimidazole, etc.), compounds having a piperidine structure (N-hydroxyethylpiperidine, bis (1,2,2,6) , 6-pentamethyl-4-piperidyl) sebacate), compounds having a pyridine structure (such as 4-dimethylaminopyridine), and compounds having an antipyrine structure (such as antipyrine and hydroxyantipyrine).
A compound having two or more ring structures is also preferably used. Specific examples include 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] -undec-7-ene.

(3) Amine compound having a phenoxy group An amine compound having a phenoxy group has a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound. Examples 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. It may have a substituent.
More preferably, it is a compound having at least one oxyalkylene chain between the phenoxy group and the nitrogen atom. The number of oxyalkylene chains in one molecule is preferably 3-9, more preferably 4-6. Among the oxyalkylene chains, —CH ₂ CH ₂ O— is preferable.
Specific examples include 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine and US Patent Application Publication No. 2007 / 0224539A1. The compounds (C1-1) to (C3-3) exemplified in paragraph [0066] of the above.

(4) Ammonium salt Ammonium salts are also used as appropriate. Preferred is hydroxide or carboxylate. More specifically, tetraalkylammonium hydroxide represented by tetrabutylammonium hydroxide is preferable. In addition, ammonium salts derived from the amines of the above (1) to (3) can be used.

  As other usable basic compounds, compounds synthesized in Examples of JP-A No. 2002-363146, compounds described in paragraph 0108 of JP-A No. 2007-298869, and the like can be used.

A basic compound is used individually or in combination of 2 or more types.
The usage-amount of a basic compound is 0.001-10 mass% normally on the basis of solid content of a composition, Preferably it is 0.01-5 mass%.

  The molar ratio of acid generator / basic compound is preferably 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoints of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to pattern thickening over time until post-exposure heat treatment. This molar ratio is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

[5] Resist solvent The solvent that can be used in preparing the composition is not particularly limited as long as it dissolves each component. For example, alkylene glycol monoalkyl ether carboxylate (propylene glycol monomethyl ether acetate (PGMEA; 1-methoxy-2-acetoxypropane)), alkylene glycol monoalkyl ether (propylene glycol monomethyl ether (PGME; 1-methoxy-2-propanol) etc.), alkyl lactate (ethyl lactate, methyl lactate etc.), cyclic lactone ( γ-butyrolactone, etc., preferably 4 to 10 carbon atoms, chain or cyclic ketone (2-heptanone, cyclohexanone, etc., preferably 4 to 10 carbon atoms), alkylene carbonate (ethylene carbonate, pro Etc. Ren carbonate), alkyl acetate such as carboxylic acid alkyl (butyl acetate is preferred), and the like alkoxy alkyl acetates (ethyl ethoxypropionate). Other usable solvents include, for example, the solvents described in US Patent Application Publication No. 2008 / 0248425A1 after [0244].

  Among the above, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether and alkyl lactate are preferable.

These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, and more preferably from 20/80 to 60/40.
As the solvent having a hydroxyl group, alkylene glycol monoalkyl ether and alkyl lactate are preferable, and as the solvent having no hydroxyl group, alkylene glycol monoalkyl ether carboxylate is preferable.

[6] Surfactant The composition of the present invention preferably further contains a surfactant. As the surfactant, fluorine-based and / or silicon-based surfactants are preferable.
Surfactants corresponding to these include Megafac F176, Megafac R08 manufactured by Dainippon Ink and Chemicals, PF656 and PF6320 manufactured by OMNOVA, Troisol S-366 manufactured by Troy Chemical Co., and Sumitomo 3M. Examples include Fluorad FC430 manufactured by Co., Ltd., polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
Further, other surfactants other than fluorine-based and / or silicon-based surfactants can also be used. More specific examples include polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.

  In addition, known surfactants can be used as appropriate. Examples of the surfactant that can be used include surfactants described in [0273] et seq. Of US Patent Application Publication No. 2008 / 0248425A1.

Surfactants may be used alone or in combination of two or more.
The amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total solid content of the composition.

[7] Other additives In addition to the components described above, the composition of the present invention has a molecular weight of 3000 or less as described in carboxylic acid, carboxylic acid onium salt, Proceeding of SPIE, 2724, 355 (1996), etc. A blocking compound, a dye, a plasticizer, a photosensitizer, a light absorber, an antioxidant, and the like can be appropriately contained.
In particular, carboxylic acid is preferably used for improving the performance. As the carboxylic acid, aromatic carboxylic acids such as benzoic acid and naphthoic acid are preferable.
The content of the carboxylic acid is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0.01 to 3% by mass in the total solid content concentration of the composition.

[8] Applications The pattern forming method of the present invention is suitably used for the production of semiconductor microcircuits such as the production of VLSI and high-capacity microchips, the production of imprint mold structures, and the like. At the time of making these, the resist film on which the pattern is formed is used for circuit formation and etching, and the remaining resist film portion is finally removed with a solvent or the like, so that it is used for a printed circuit board or the like. Unlike so-called permanent resists, the resist film derived from the resist composition described in the present invention does not remain in the final product.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, the content of this invention is not limited by this.

1. Example of composition material composition (1) Resin (component A)
Synthesis Example 1 (Synthesis of Resin Example (33))
3.9 g (0.024 mol) of 3-acetoxystyrene and 0.8 g (0.006 mol) of 4-methoxystyrene were dissolved in 30 ml of 1-methoxy-2-propanol at 70 ° C. under a nitrogen stream and stirring. Polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd .; trade name V-65) 50 mg, 3-acetoxystyrene 9.1 g (0.056 mol), A solution of 1.9 g (0.014 mol) of 4-methoxystyrene in 70 ml of 1-methoxy-2-propanol was added dropwise over 2 hours. Two hours later, 50 mg of initiator was added, and the reaction was further performed for 2 hours. Thereafter, the temperature was raised to 90 ° C. and stirring was continued for 1 hour. The reaction solution was allowed to cool and then poured into 1 L of ion exchange water with vigorous stirring to precipitate a white resin. The obtained resin was dried, dissolved in 100 mL of methanol, 25% tetramethylammonium hydroxide was added, the acetoxy group in the resin was hydrolyzed, and then neutralized with an aqueous hydrochloric acid solution to precipitate a white resin. After washing with ion-exchanged water and drying under reduced pressure, 11.6 g of the resin (33) of the present invention was obtained. When the molecular weight was measured by GPC, it was 9,200 in terms of weight average (Mw: polystyrene conversion) and 2.0 in terms of dispersity (Mw / Mn).
Hereinafter, each resin of the component (A) of the present invention was synthesized in the same manner.

(2) Synthesis of crosslinking agent (component B)
Synthesis of (HM-1) 20 g of 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4- [α, α-bis (4-hydroxyphenyl) ethyl] benzene (Honshu Chemical Industry Co., Ltd.) Trisp-PA) was added to a 10% aqueous potassium hydroxide solution, and stirred and dissolved. Next, 60 ml of 37% formalin aqueous solution was gradually added over 1 hour at room temperature while stirring this solution. The mixture was further stirred for 6 hours at room temperature and then poured into a dilute sulfuric acid aqueous solution. The precipitate was filtered, sufficiently washed with water, and then recrystallized from 30 ml of methanol to obtain 20 g of a white powder of a phenol derivative [HM-1] having a hydroxymethyl group having the following structure. The purity was 92% (liquid chromatography method).

Synthesis of (MM-1) 20 g of the phenol derivative [HM-1] having a hydroxymethyl group obtained in the above synthesis example was added to 1 liter of methanol and dissolved by heating under stirring. Next, 1 ml of concentrated sulfuric acid was added to this solution and heated under reflux for 12 hours. After completion of the reaction, the reaction solution was cooled and 2 g of potassium carbonate was added. After sufficiently concentrating the mixture, 300 ml of ethyl acetate was added. The solution was washed with water and then concentrated to dryness to obtain 22 g of a phenol derivative [MM-1] having a methoxymethyl group having the following structure as a white solid. The purity was 90% (liquid chromatography method).

  Further, the following phenol derivatives were synthesized in the same manner.

2. Examples 2.1 EB exposure (1) Preparation and coating of negative resist coating solution A coating solution having the composition shown in Table 2 was precisely filtered with a membrane filter having a pore size of 0.1 μm to obtain a resist solution. . In Table 2, the ratio when two or more components are used is a mass ratio.
This resist solution is applied onto a 6-inch Si wafer subjected to HMDS treatment using a spin coater Mark8 manufactured by Tokyo Electron and dried on a hot plate at 110 ° C. for 90 seconds to obtain a resist film having a thickness of 0.1 μm. It was.

(2) EB exposure evaluation The resist film obtained in the above (1) was subjected to pattern irradiation using an electron beam drawing apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage 50 KeV). After irradiation, it was heated on a hot plate at 120 ° C. for 90 seconds.
Subsequently, ADE-3000S (manufactured by Actis) was used as a solvent developing device, spray development was performed while rotating the wafer at 1000 rpm for 30 seconds at a flow rate of 200 mL / min using the organic solvent shown in Table 3, and then 2000 rotations (Rpm) was rotated at high speed for 20 seconds to dry.
If the solvent is specified in the rinse liquid item, spray development is performed for 30 seconds at a flow rate of 200 mL / min using an organic solvent, and then the wafer is rotated at 1500 rpm (rpm) for the specified organic solvent. Then, rinsing was performed at a flow rate of 200 mL / min for 30 seconds, and then, high-speed rotation was performed at 3000 rpm (rpm) for 20 seconds to dry.

The obtained patterns were evaluated for sensitivity, resolving power, dimensions before falling, and line width roughness by the following methods. The evaluation results are shown in Table 4 below.
In addition, the measurement of the dissolution rate of the resist film by the good solvent or the poor solvent used as the developer was performed as follows and is shown in Table 4.
(2-1) Dissolution rate A good solvent or a poor solvent respectively used as a developer on a wafer having a resist film prepared with the resist composition described in Table 3 under the conditions described in (1) above at a flow rate of 200 mL / min. After spray development while rotating the wafer at 1000 rpm for 5 seconds, the wafer was rotated at high speed for 20 seconds at 3000 rpm (rpm), and further heated on a hot plate at 90 ° C. for 60 seconds for drying. Then, the film thickness was measured using VM8000-200 (Dainippon Screen manufacture).
The dissolution rate was calculated from the change in film thickness before and after development. The film pressure was measured in a clean room at 23 ° C. and a relative humidity of 50%.
Dissolution rate = Amount of change in film thickness before and after development for 5 seconds / 5 seconds (2-2) Sensitivity (E ₀ )
The obtained pattern was observed using a scanning electron microscope (S-9220 manufactured by Hitachi, Ltd.). The electron beam irradiation dose when resolving 0.10 μm (line: space = 1: 1) was defined as sensitivity (E ₀ ).

(2-3) Resolving power The limiting resolving power (minimum line width at which lines and spaces are separated and resolved) at the exposure amount showing the above sensitivity was defined as resolving power.

(2-4) Dimensions before falling The pattern size at which pattern collapse occurs when the exposure dose is reduced from the irradiation amount (E ₀ ) showing the above sensitivity under the same conditions as the sensitivity measurement is defined as the dimension before falling. The dimensions before collapse were evaluated as an index of process margin.

(2-5) Line width roughness (LWR)
The line width was measured at arbitrary 30 points in the length direction of 50 μm of the 0.10 μm line pattern at the irradiation dose showing the above sensitivity, and the variation was evaluated at 3σ (nm).

[Examples 1 to 9]
Using each component shown in Table 2 below, a resist solution was prepared as described above, and a pattern was formed using the developer shown in Table 3.
[Comparative Example 1]
As shown in Table 3, a resist solution was prepared and a pattern was formed in the same manner as in Example except that development was performed using an alkaline aqueous solution (TMAH; tetramethylammonium hydroxide (2.38 mass%) aqueous solution). .

[Reference Example 2]
As shown in Table 3, a resist solution was prepared and a pattern was formed in the same manner as in Example except that development was performed with butyl acetate alone.

[Reference Example 3]
As shown in Table 3, a resist solution was prepared and a pattern was formed in the same manner as in Example except that development was performed with 1-octanol and decane mixed solvent.
Table 1 shows the boiling point of each solvent used.

<Organic basic compound>
D-1: Tetra- (n-butyl) ammonium hydroxide D-2: 1,8-diazabicyclo [5.4.0] -7-undecene D-3: Tridodecylamine

<Resist solvent>
S-1: Propylene glycol monomethyl ether acetate (PGMEA)
S-2: Propylene glycol monomethyl ether (PGME)
S-3: Ethyl lactate (EL)

<Surfactant>
W-1: PF6320 (manufactured by OMNOVA)
W-2: Mega-Fack F176 (Dainippon Ink Chemical Co., Ltd.)

2.2 EUV exposure (3) Preparation and coating of negative resist coating solution
The coating liquid composition shown in Table 5 was microfiltered with a membrane filter having a pore size of 0.1 μm to obtain a resist solution.
This resist solution is applied onto a 6-inch Si wafer subjected to HMDS treatment using a spin coater Mark8 manufactured by Tokyo Electron and dried on a hot plate at 110 ° C. for 90 seconds to obtain a resist film having a thickness of 0.1 μm. It was.

(4) Evaluation of EUV exposure Surface exposure was performed using EUV light (wavelength 13 nm) on this resist film while changing the exposure amount in increments of 0.5 mJ within a range of 0 to 10.0 mJ.
After irradiation, it was heated on a hot plate at 120 ° C. for 90 seconds.
Subsequently, the organic solvent shown in Table 6 was used for spray development for 30 seconds at a flow rate of 200 mL / min, and then dried by high-speed rotation for 20 seconds at 2000 rpm (rpm).
If a solvent is specified in the rinse liquid item, spray development is performed using an organic solvent at a flow rate of 200 mL / min for 30 seconds, and then the specified organic solvent is further rotated at 1500 rpm (rpm). Then, rinsing was performed at a flow rate of 200 mL / min for 30 seconds, and then, high speed rotation was performed at 2000 rpm (rpm) for 20 seconds to dry.
Using the obtained sensitivity-residual film ratio curve, the sensitivity (Eth) and the residual film ratio were evaluated by the following methods.
(4-1) Sensitivity (Eth)
The exposure amount at which the remaining film ratio was 50% was defined as sensitivity (Eth).
(4-2) Residual film ratio Further, (film thickness after development / film thickness before exposure) × 100 at an irradiation dose three times the obtained sensitivity (Eth) was defined as a residual film ratio (%).
[Examples 10 to 17]
Using each component shown in Table 5 below, a resist solution was prepared and a pattern was formed as described above.
In Table 5, the ratio when two or more components are used is a mass ratio. The evaluation results are shown in Table 7 below.
In Table 5, each abbreviation shows the same abbreviation in Table 2.

  From Tables 4 and 7, it can be seen that the pattern forming method using the negative resist composition of the present invention has excellent sensitivity, resolution, dimension before collapse, and remaining film ratio, and has good performance. In particular, it can be seen that the line width roughness is greatly improved in EB exposure while having good performance in terms of resolving power and dimensions before tilting.

Claims (14)

A step (1) of forming a resist film using a negative chemically amplified resist composition that is negativeized by a crosslinking reaction, a step (2) of exposing the film, and developing using a developer containing an organic solvent after the exposure. In the method for forming a resist pattern, characterized by comprising the steps (4) in this order:
The developing solution in step (4) is an organic solvent, a solvent (S-1) that is a good solvent for the resist film before exposure and a solvent (S-2) that is a poor solvent for the resist film before exposure. Contains,
Resist pattern formation characterized by satisfying the relationship of formula (A) where the boiling point of the solvent (S-1) is (bp-1) and the boiling point of the solvent (S-2) is (bp-2) Method.
(Bp-2)> (bp-1) Formula (A)   The resist pattern forming method according to claim 1, wherein the solvent (S-1) is an ester solvent, a ketone solvent, or an ether solvent.   The resist pattern forming method according to claim 1, wherein the solvent (S-2) is a hydrocarbon solvent.   The resist pattern forming method according to claim 1, wherein the solvent (S-2) has a boiling point of 150 ° C. or higher.   The resist pattern forming method according to claim 1, wherein the exposure step (2) is performed by an electron beam or EUV light.   The resist pattern forming method according to claim 1, wherein the resist pattern forming method is for forming a semiconductor fine circuit.   A negative chemically amplified resist composition that is negatively formed by a crosslinking reaction comprises (A) a resin, (B) a crosslinking agent that crosslinks the resin (A) by the action of an acid, and (C) irradiation with actinic rays or radiation. The pattern forming method according to claim 1, comprising a compound that generates an acid. The pattern forming method according to claim 7, wherein the resin (A) is a resin containing a repeating unit represented by the general formula (1).

In formula (1),
A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group.
When a plurality of R ₁ are present, each independently represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group or an alkylcarbonyloxy group.
a represents an integer of 1 to 3.
b represents an integer of 0 to (3-a). The pattern forming method according to claim 7, wherein the crosslinking agent (B) is a phenol compound.   The pattern forming method according to claim 9, wherein the crosslinking agent (B) is a phenol compound having two or more benzene rings in the molecule.   The pattern forming method according to claim 9 or 10, wherein the crosslinking agent (B) is a phenol compound having 2 to 8 crosslinking groups per molecule capable of crosslinking the resin (A).   The compound (C) is a compound that generates at least one of sulfonic acid, bis (alkylsulfonyl) imide, and tris (alkylsulfonyl) methide upon irradiation with actinic rays or radiation. Item 12. The resist pattern forming method according to any one of Items 7 to 11.   A developer for use in the pattern forming method according to claim 1. A crosslinkable negative chemically amplified resist composition for organic solvent development, which is used in the pattern forming method according to claim 1.