JP5444668B2 - Resist pattern forming method - Google Patents

Description

The present invention relates to a method of forming a micro fine resist pattern.

  In the field of microfabrication represented by the manufacture of integrated circuit elements, in order to obtain a higher degree of integration, recently, lithography technology capable of microfabrication at a level of 0.10 μm or less is required. However, in the conventional lithography process, near-ultraviolet rays such as i-rays are generally used as radiation, and it is said that fine processing at a subquarter micron level is extremely difficult with this near-ultraviolet rays. Therefore, in order to enable microfabrication at a level of 0.10 μm or less, use of radiation having a shorter wavelength is being studied. Examples of such short-wavelength radiation include an emission line spectrum of a mercury lamp, far-ultraviolet rays typified by an excimer laser, an X-ray, an electron beam, and the like. Among these, a KrF excimer laser (wavelength 248 nm) is particularly preferable. ) Or ArF excimer laser (wavelength 193 nm) has been attracting attention.

  As a resist suitable for irradiation with such an excimer laser, a component having an acid dissociable functional group and a component that generates an acid upon irradiation with radiation (hereinafter also referred to as “exposure”) (hereinafter referred to as “acid generator”) Many resists using the chemical amplification effect (hereinafter also referred to as “chemically amplified resist”) have been proposed. As the chemically amplified resist, for example, a resist containing a resin having a tert-butyl ester group of carboxylic acid or a tert-butyl carbonate group of phenol and an acid generator has been proposed (see, for example, Patent Document 1). ). In this resist, the tert-butyl ester group or tert-butyl carbonate group present in the resin is dissociated by the action of an acid generated by exposure, and the resin has an acidic group composed of a carboxyl group or a phenolic hydroxyl group. As a result, the phenomenon that the exposed region of the resist film becomes readily soluble in an alkali developer is utilized.

  In such a lithography process, further fine pattern formation (for example, a fine resist pattern having a line width of about 45 nm) will be required in the future. In order to achieve such fine pattern formation of less than 45 nm, it is conceivable to shorten the light source wavelength of the exposure apparatus and increase the numerical aperture (NA) of the lens as described above. However, a new expensive exposure apparatus is required to shorten the light source wavelength. Further, when the lens has a high NA, the resolution and the depth of focus are in a trade-off relationship. Therefore, there is a problem that the depth of focus decreases even if the resolution is increased.

  Recently, as a lithography technique capable of solving such a problem, a method called an immersion exposure (liquid immersion lithography) method has been reported (for example, see Patent Document 2). In this method, at the time of exposure, a liquid high refractive index medium (immersion exposure liquid) such as pure water or a fluorine-based inert liquid having a predetermined thickness on at least the resist film between the lens and the resist film on the substrate. Is to intervene. In this method, a light source having the same exposure wavelength can be used by replacing the exposure optical path space, which has conventionally been an inert gas such as air or nitrogen, with a liquid having a higher refractive index (n), such as pure water. Similar to the case of using a light source with a shorter wavelength or the case of using a high NA lens, high resolution is achieved and there is no reduction in the depth of focus. If such immersion exposure is used, it is possible to realize the formation of a resist pattern that is low in cost, excellent in high resolution, and excellent in depth of focus, using a lens mounted on an existing apparatus. It has attracted a great deal of attention and is being put to practical use.

  However, it is said that the extension of the above-described exposure technique is limited to 45 nmhp, and technical development for the 32 nmhp generation that requires further fine processing is being carried out. In recent years, with the demand for higher complexity and higher density of such devices, a technique for patterning 32 nm LS by sparse line patterns such as double patterning or double exposure or by overlapping half-cycles of isolated trench patterns has been proposed. (For example, refer nonpatent literature 1).

  In Non-Patent Document 1, a 32 nm line having a pitch of 1: 3 is formed and then processed by etching, and a 32 nm line having a pitch of 1: 3 is similarly formed at a position shifted by a half period from the first resist pattern. It is disclosed that it is formed and processed again by etching to finally form a 32 nm line with a 1: 1 pitch.

Japanese Patent Laid-Open No. 5-232704 JP-A-10-303114 SPIE 2006 Vol. 6153 6153K

  However, although there are proposals for several processes as described above, no proposals for more specific and practical methods and materials have been made yet.

The present invention has been made in view of the problems of the prior art, and has as its object, the resist pattern forming how capable of forming a finer resist pattern easily and efficiently Is to provide.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have developed a resist pattern formed using a positive radiation-sensitive resin composition containing a resin containing a predetermined unit of repeating units having a specific structure. After the insolubilization, it was found that the above-mentioned problems can be achieved by forming a resist pattern, and the present invention has been completed.

That is, according to the present invention, shown to Les resist pattern forming method is provided below.

（前記一般式（１）中、Ｒ ^１ は、水素又はメチル基を示し、複数のＲ ^２ は、（ｉ）相互に独立して、炭素数４〜２０の１価の脂環式炭化水素基若しくはその誘導体、又は炭素数１〜４の直鎖状若しくは分岐状のアルキル基を示す（但し、Ｒ ^２ の少なくとも１つは炭素数７〜２０の１価の多環式炭化水素基である）か、或いは（ｉｉ）いずれか２つのＲ ^２ が相互に結合して形成される、それぞれが結合している炭素原子を含む炭素数７〜２０の２価の多環式炭化水素基を示し、残りのＲ ^２ が、炭素数１〜４の直鎖状若しくは分岐状のアルキル基、又は炭素数４〜２０の１価の脂環式炭化水素基若しくはその誘導体を示す）

（前記一般式（ｉ）中、Ｒ ^３０ は、水素原子、フッ素原子、メチル基又はトリフルオロメチル基を表す。Ｒ ^３１ は、炭素数１〜１０のエーテル結合、エステル結合、カルボニル基、水酸基、又は不飽和結合を含んでもよい二価の有機基を表す。Ｒ ^３２ 、Ｒ ^３３ はそれぞれ独立に水素原子、又は炭素数１〜１０のエーテル結合、エステル結合、カルボニル基、水酸基、又は不飽和結合を含んでもよい一価の有機基を表す。Ｒ ^３１ とＲ ^３２ 又はＲ ^３１ とＲ ^３３ は互いに結合してこれらが結合する（即ち、Ｒ ^３１ とＲ ^３３ の場合は直接結合する、Ｒ ^３２ の場合は酸素原子を介して結合する）炭素原子と共に環を形成してもよく、この場合、Ｒ ^３１ とＲ ^３２ 又はＲ ^３１ とＲ ^３３ を合わせて炭素数２〜２０の三価の有機基を表す。Ｒ ^３２ とＲ ^３３ は互いに結合してこれらが結合する（即ち、Ｒ ^３２ の場合は酸素原子を介して結合する、Ｒ ^３３ の場合は直接結合する）炭素原子と共に環を形成してもよく、この場合、Ｒ ^３２ とＲ ^３３ を合わせて炭素数２〜２０の二価の有機基を表す。Ｘ’は水酸基、ハロゲン原子、又は炭素数１〜１０のエーテル結合、エステル結合、カルボニル基、水酸基、又は不飽和結合を含んでもよい一価の有機基を表す。ｎ’は０〜７の整数を表す。））

［２］前記一般式（１）中の−Ｃ（Ｒ ^２ ） _３ で表される基が、下記一般式（１ａ）、（１ｂ）、（１ｄ）、又は（１ｅ）で表される基である前記［１］に記載のレジストパターン形成方法。

（前記一般式（１ａ）、（１ｂ）、（１ｄ）、及び（１ｅ）中、Ｒ ^３ は、相互に独立して、炭素数１〜４の直鎖状又は分岐状のアルキル基である。）
［３］前記レジストパターン不溶化樹脂組成物に含まれるアルコール溶媒が、炭素数１〜８の１価アルコールである前記［１］又は［２］に記載のレジストパターン形成方法。
［４］前記レジストパターン不溶化樹脂組成物に含まれる水酸基を含有する樹脂が、下記一般式（７）で表される単量体成分を重合して得られる樹脂である前記［１］〜［３］のいずれかに記載のレジストパターン形成方法。

（前記一般式（７）中、Ｒ ^１３ は、相互に独立に、水素原子、又はメチル基を示し、Ｒ ^１４ は、単結合、又は直鎖状、分岐状若しくは環状の２価の炭化水素基を示す。）
［５］前記レジストパターン不溶化樹脂組成物に含まれる水酸基を含有する樹脂が、さらに下記一般式（８−１）で表される単量体と下記一般式（８−２）で表される単量体の少なくともいずれかを重合して得られる樹脂である前記［４］に記載のレジストパターン形成方法。

（前記一般式（８−１）中、Ｒ ^１５ は、水素原子、メチル基、又はトリフルオロメチル基を示し、Ａは、メチレン基、エチレン基、又はプロピレン基を示し、Ｒ ^１６ は、下記式（９−１）で表される基、又は下記式（９−２）で表される基を示す。また、前記一般式（８−２）中、Ｒ ^１５ は、水素原子、メチル基、又はトリフルオロメチル基を示し、Ｒ ^１７ は、メチレン基、又は炭素数２〜６のアルキレン基を示し、Ｒ ^１８ は、水素原子、メチル基、又はエチル基を示し、ｎは、０又は１を示す。）

[ 1 ] (1) The first resist layer formed on the substrate using the first positive-type radiation-sensitive resin composition is selectively exposed through a mask and then developed to develop a first resist. And (2) applying a resist pattern insolubilized resin composition containing a hydroxyl group-containing resin and an alcohol solvent on the first resist pattern, and baking or UV curing, followed by washing, A step of making the first resist pattern an insolubilized resist pattern insoluble in a developer and a second positive radiation sensitive resin composition; and (3) a second positive radiation sensitive resin composition. Forming a second resist layer on the insolubilized resist pattern and selectively exposing the second resist layer through a mask; and (4) developing to form a second resist pattern. Craft When, wherein the said first positive-tone radiation-sensitive resin composition used in step (1) is an acid containing 5 to 65 mole percent of repeating units of one or more kinds represented by the following general formula (1) Positive-type radiation-sensitive resin composition containing a resin having a dissociable group (however, the resin having an acid-dissociable group contains a repeating unit obtained from a monomer represented by the following general formula (i) A resist pattern forming method which is a polymer compound, a polymer compound represented by the following formula (ii), and a polymer compound represented by the following formulas (iii-1) to (iii-5) .

(In the general formula (1), R ¹ represents hydrogen or a methyl group, and a plurality of R ² are (i) each independently, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms. Or a derivative thereof, or a linear or branched alkyl group having 1 to 4 carbon atoms (provided that at least one of R ² is a monovalent polycyclic hydrocarbon group having 7 to 20 carbon atoms) Or (ii) a divalent polycyclic hydrocarbon group having 7 to 20 carbon atoms, each of which is formed by bonding any two of R ^{2 s} to each other, and containing each bonded carbon atom; The remaining R ² represents a linear or branched alkyl group having 1 to 4 carbon atoms, or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof.

(In the general formula (i), R ³⁰ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ³¹ represents an ether bond, ester bond, carbonyl group, hydroxyl group, Or a divalent organic group that may contain an unsaturated bond, R ³² and R ³³ are each independently a hydrogen atom, or an ether bond, an ester bond, a carbonyl group, a hydroxyl group, or an unsaturated bond having 1 to 10 carbon atoms. the containing ^{.R 31} and ^{R 32} or ^{R 31} and ^{R 33} also represents an univalent organic group is binding to which they are attached to one another ^(i.e., in the case of ^{R 31} and ^{R 33} directly ^bonded, the ^{R 32} In this case, a trivalent organic group having 2 to 20 carbon atoms may be formed by combining R ³¹ and R ³² or R ³¹ and R ^33. representing ^{.R 32} and ³³ coupled to which they are attached to one another (i.e., in the case of R ³² is attached via an oxygen atom, directly attached in the case of R ³³⁾ may form a ring together with the carbon atoms, in this case, R ³² and R ³³ together represent a divalent organic group having 2 to 20 carbon atoms, X ′ being a hydroxyl group, a halogen atom, or an ether bond, ester bond, carbonyl group, hydroxyl group, or unsaturated group having 1 to 10 carbon atoms. Represents a monovalent organic group which may contain a bond, and n ′ represents an integer of 0 to 7.))

[2] The group represented by —C (R ² ) ₃ in the general formula (1) is a group represented by the following general formula (1a), (1b), (1d), or (1e). The resist pattern forming method according to [1].

(In said general formula (1a), (1b), (1d), and (1e), R < ³ > is a C1-C4 linear or branched alkyl group mutually independently. )
[3] The resist pattern forming method according to [1] or [2], wherein the alcohol solvent contained in the resist pattern insolubilized resin composition is a monohydric alcohol having 1 to 8 carbon atoms.
[4] The above [1] to [3], wherein the resin containing a hydroxyl group contained in the resist pattern insolubilized resin composition is a resin obtained by polymerizing a monomer component represented by the following general formula (7). ] The resist pattern formation method in any one of.

(In the general formula (7), R ¹³ independently represents a hydrogen atom or a methyl group, and R ¹⁴ represents a single bond or a linear, branched or cyclic divalent hydrocarbon group. Is shown.)
[5] Resin containing a hydroxyl group contained in the resist pattern insolubilized resin composition is a monomer represented by the following general formula (8-1) and a single monomer represented by the following general formula (8-2). The method for forming a resist pattern according to the above [4], which is a resin obtained by polymerizing at least one of the monomers.

(In the general formula (8-1), R ¹⁵ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, A represents a methylene group, an ethylene group, or a propylene group, and R ¹⁶ represents the following formula: A group represented by (9-1) or a group represented by the following formula (9-2), and in the general formula (8-2), R ¹⁵ represents a hydrogen atom, a methyl group, or Represents a trifluoromethyl group, R ¹⁷ represents a methylene group or an alkylene group having 2 to 6 carbon atoms, R ¹⁸ represents a hydrogen atom, a methyl group or an ethyl group, and n represents 0 or 1 .)

  According to the resist pattern forming method of the present invention, a finer resist pattern can be easily and efficiently formed.

  BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the present invention will be described below, but the present invention is not limited to the following embodiment, and is based on the ordinary knowledge of those skilled in the art without departing from the gist of the present invention. It should be understood that modifications and improvements as appropriate to the following embodiments also fall within the scope of the present invention. Hereinafter, the “first positive radiation sensitive resin composition” and the “second positive radiation sensitive resin composition” are also simply referred to as “first resist agent” and “second resist agent”, respectively. The “resist pattern insolubilized resin composition” is also simply referred to as “insolubilized resin composition”.

1. Resist pattern formation method:
((1) Process)
In the step (1), a first resist, which will be described later, is applied to a silicon wafer or a substrate such as a wafer coated with SiN or an organic antireflection film by an appropriate application means such as spin coating, cast coating, or roll coating. agent (Po di-tone radiation-sensitive resin composition) is applied. Thereby, the 1st resist layer which consists of a 1st resist agent can be formed. In addition, after apply | coating a 1st resist agent, you may volatilize the solvent in a coating film by prebaking (PB) as needed. Although the prebaking heating conditions are appropriately selected depending on the composition of the first resist agent, they are usually 30 to 200 ° C, preferably 50 to 150 ° C.

  In order to maximize the potential of the first resist agent, an organic or inorganic antireflection film is formed on the substrate as disclosed in, for example, Japanese Patent Publication No. 6-12458. It ’s good to leave. In order to prevent the influence of basic impurities contained in the environmental atmosphere, it is also preferable to provide a protective film on the first resist layer as disclosed in, for example, JP-A-5-188598. . It is also preferable to perform both formation of the antireflection film and formation of the protective film.

  The required region of the formed first resist layer is exposed by irradiating with radiation through a mask having a predetermined pattern to form a pattern latent image portion (portion that has become insoluble in alkali by exposure). The radiation used is appropriately selected from visible rays, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, etc., depending on the type of acid generator contained in the first resist agent, but ArF excimer laser ( Far ultraviolet rays typified by a wavelength of 193 nm) and KrF excimer laser (wavelength 248 nm) are preferred, and an ArF excimer laser (wavelength 193 nm) is particularly preferred. In addition, exposure conditions, such as exposure amount, are suitably selected according to the compounding composition of a 1st resist agent, the kind of additive, etc. Furthermore, in this invention, it is preferable to perform heat processing (PEB) after exposure. By this PEB, the dissociation reaction of the acid dissociable group in the resin component can be smoothly advanced. The heating conditions for PEB are appropriately selected depending on the composition of the resin composition, but are usually 30 to 200 ° C, preferably 50 to 170 ° C.

By developing the exposed first resist layer, the pattern latent image portion is exposed, and a positive first resist pattern having a predetermined line width L ₁ and having a predetermined space portion as shown in FIG. 1 is formed on the substrate 10. Examples of the developer that can be used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, and di-n-propylamine. , Triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- An alkaline aqueous solution in which at least one of alkaline compounds such as [4.3.0] -5-nonene is dissolved is preferable. The concentration of the alkaline aqueous solution is usually 10% by mass or less. When the concentration of the alkaline aqueous solution exceeds 10% by mass, the non-exposed portion tends to be easily dissolved in the developer. In addition, after developing using alkaline aqueous solution, generally it wash | cleans with water and dries.

  An organic solvent can also be added to the alkaline aqueous solution (developer). Examples of the organic solvent that can be added include ketones such as acetone, methyl ethyl ketone, methyl i-butyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, and 2,6-dimethylcyclohexanone; methyl alcohol, ethyl alcohol , N-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol, 1,4-hexanedimethylol, and the like; tetrahydrofuran, dioxane Ethers such as ethyl acetate, n-butyl acetate, i-amyl acetate, aromatic hydrocarbons such as toluene and xylene, phenol, acetonylacetone, dimethylformamide, etc. That. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

  The addition amount of the organic solvent is preferably 100 parts by volume or less with respect to 100 parts by volume of the alkaline aqueous solution. When the addition amount of the organic solvent is more than 100 parts by volume with respect to 100 parts by volume of the alkaline aqueous solution, the developability may be deteriorated and the development residue in the exposed part may increase. An appropriate amount of a surfactant or the like can be added to the developer.

((2) Process)
In the step (2), an insolubilized resin composition to be described later is applied onto the formed first resist pattern by an appropriate application means such as spin coating, cast coating, or roll coating. At this time, the insolubilized resin composition is applied so that the first resist pattern is covered. After applying the insolubilized resin composition, heat treatment (baking) or UV curing is performed. By this heat treatment or UV curing, the first resist pattern is reacted with the applied insolubilized resin composition. Although heating conditions are suitably selected by the compounding composition of an insolubilized resin composition, they are 30-200 degreeC normally, Preferably it is 50-170 degreeC. On the other hand, for UV curing, lamps such as Ar ₂ lamp, KrCl lamp, Kr ₂ lamp, XeCl lamp, Xe ₂ lamp (USHIO Inc.) can be used. After appropriately cooling and developing in the same manner as in the above step (1), the surface of the first resist pattern 1 is an insoluble film 5 made of a resin composition as shown in FIGS. The insolubilized resist pattern 3 that is a line-and-space pattern having the first line portion 1a and the first space portion 1b that is covered can be formed. The insolubilized resist pattern 3 (first line portion 1a) to be formed is insoluble or hardly soluble in the developer and the second resist agent. After development, the insolubilized resist pattern may be cured a plurality of times by heat treatment (PEB) or UV curing as necessary.

  The insolubilized first resist pattern 1 (insolubilized resist pattern 3) remains in the pattern shape even when the second resist agent is applied, exposed and developed in the following steps (3) and (4). . However, the pattern width may slightly change depending on the thickness of the applied insolubilized resin composition. In addition, you may perform this (2) process in multiple times as needed.

((3) Process)
In the step (3), as shown in FIG. 4, a second resist agent is applied onto the insolubilized resist pattern 3 formed on the substrate 10 by an appropriate application means such as spin coating, cast coating, roll coating or the like. Then, the second resist layer 12 made of the second resist agent is formed. Thereafter, as in the case of step (1), pre-baking (PB) may be performed as necessary. Next, in the same manner as in the step (1), the second resist layer 12 and, if necessary, the space portion of the first resist pattern (insolubilized resist pattern 3) are selectively exposed through a mask. Note that heat treatment (PEB) may be further performed as necessary.

((4) Process)
In the step (4), a positive second resist pattern is formed by developing in the same manner as in the step (1). Through the above steps, a resist pattern having a configuration in which a first resist pattern (insolubilized resist pattern) and a second resist pattern are sequentially added on the substrate can be formed. If the resist pattern formed in this way is used, a semiconductor can be manufactured.

  In the above-described step (3), various resist patterns having a characteristic pattern arrangement can be finally formed by appropriately selecting a mask pattern used for selective exposure. For example, as shown in FIG. 5, when the insolubilized resist pattern 3 having the first line portion 1a and the first space portion 1b is formed, the mask pattern used in the exposure in the step (3) is selected to select the second pattern. The second line portion 2a of the second resist pattern 2 having the line portion 2a and the second space portion 2b can be formed in the first space portion 1b in parallel with the first line portion 1a.

  For example, as shown in FIG. 6, the second line of the second resist pattern 22 having the second line portion 22a and the second space portion 22b is selected by selecting a mask pattern used in the exposure in the step (3). If the portion 22a is formed in a grid pattern in the first space portion 1b, a resist pattern (contact hole pattern) having the contact hole 15 defined by the first line portion 1a and the second line portion 22a of the insolubilized resist pattern is formed. be able to.

  Further, for example, as shown in FIGS. 7 and 8, if the mask pattern used in the exposure in the step (3) is selected, the second resist pattern 32 having the second line portion 32a and the second space portion 32b is selected. The two line portions 32a can be formed on the first line portion 1a so as to intersect the first line portion 1a.

2. Positive type radiation sensitive resin composition:
The “first positive radiation-sensitive resin composition (first resist agent)” and “second positive radiation-sensitive resin composition (second resist agent)” used in the above-described resist pattern forming method are: In any case, due to the action of the acid generated from the acid generator by exposure, the acid dissociable groups contained therein are dissociated, and the exposed portion of the resist whose solubility in the alkali developer is increased is dissolved in the alkali developer. It is removed and a positive resist pattern can be obtained. The first resist agent and the second resist agent both contain a resin having an acid dissociable group. Furthermore, as other components, a radiation-sensitive acid generator (hereinafter also referred to as “acid generator”) and a solvent are usually contained. Hereinafter, details of the first resist agent will be described, but the details of the second resist agent are the same, and the first resist agent and the second resist agent may be the same or different. . Hereinafter, the term “resist agent” means both “first resist agent” and “second resist agent”.

(Resin having an acid dissociable group)
Resins having an acid dissociable group are those comprising repeating units of one or more kinds represented by the general formula (1). However, the polymer compound containing the repeating unit obtained from the monomer represented by the general formula (i), the polymer compound represented by the formula (ii), and the formulas (iii-1) to (iii) The polymer compound represented by -5) is excluded.

In the general formula (1), a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R ² carbon atoms and any two of R ² is formed by bonding to each other, 4-20 Specific examples of the divalent alicyclic hydrocarbon group include fatty acids derived from cycloalkanes such as norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. A group consisting of a cyclic ring; a group consisting of these alicyclic rings is, for example, a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methyl Examples include a group substituted with one or more linear, branched, or cyclic alkyl groups having 1 to 4 carbon atoms such as a propyl group and a t-butyl group. Of these, a group consisting of an alicyclic ring derived from norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclopentane, or cyclohexane, or a group obtained by substituting these with the above alkyl group is preferable.

In the general formula (1), specific examples of the derivative of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R ² include a hydroxyl group; a carboxyl group; an oxo group (that is, a ═O group). ); Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3- A hydroxyalkyl group having 1 to 4 carbon atoms such as hydroxybutyl group and 4-hydroxybutyl group; methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1- C1-C4 alkoxyl groups such as methylpropoxy group and t-butoxy group; cyano group; cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group The group which has 1 or more types of substituents, such as C2-C5 cyanoalkyl groups, such as a propyl group and 4-cyanobutyl group, can be mentioned. Of these, a hydroxyl group, a carboxyl group, a hydroxymethyl group, a cyano group, and a cyanomethyl group are preferable.

In the general formula (1), specific examples of the linear or branched alkyl group having 1 to 4 carbon atoms represented by R ² include a methyl group, an ethyl group, an n-propyl group, and i-propyl. Group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like. Of these, a methyl group and an ethyl group are preferable.

In the general formula (1), "- ^{C (R} _{2) 3"} Specific examples of the group represented by the general formula (1a), the general formula (1b), the general formula (1d), or The group represented by the general formula (1e) can be exemplified .

In the general formulas (1a) to (1e), R ³ is independently a linear or branched alkyl group having 1 to 4 carbon atoms, and m is 0 or 1. Specific examples of the linear or branched alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1- Examples thereof include a methylpropyl group and a t-butyl group. Of these, a methyl group and an ethyl group are preferable.

In the general formula (1), a portion represented by “—COOC (R ² ) ₃ ” is a portion that is dissociated by the action of an acid to form a carboxyl group and becomes an alkali-soluble portion. This “alkali-soluble site” is a group that becomes an anion (alkali-soluble) by the action of an alkali. On the other hand, an “acid-dissociable group” is a group in which an alkali-soluble site is protected with a protecting group, and is a group that is not “alkali-soluble” until the protecting group is removed with an acid.

  The resin having an acid-dissociable group is a resin that is itself insoluble in alkali or hardly soluble in alkali, but becomes alkali-soluble by the action of an acid. Here, “alkali insoluble or hardly soluble in alkali” means development conditions for forming a resist pattern using a resist layer comprising a resist agent containing a resin having a repeating unit represented by the general formula (1). In the case where a film made of only the resin containing the repeating unit represented by the general formula (1) is processed (but not exposed), 50% or more of the initial film thickness remains after the processing. Refers to nature. On the other hand, “alkali-soluble” refers to a property in which 50% or more of the initial film thickness of the film is lost after the same treatment.

  The ratio of the one or more repeating units represented by the general formula (1) contained in the resin having an acid dissociable group is 5 to 65 mol%, preferably 10 to 60 mol%, more preferably 15 ˜50 mol%. Even if it uses the insolubilized resin composition mentioned later that the content rate of the 1 or more types of repeating unit represented by the said General formula (1) is less than 5 mol% or more than 65 mol%, a 1st resist pattern is used. It may be difficult to sufficiently insolubilize. Moreover, it may be difficult to obtain a sufficiently insoluble resist pattern that is sufficiently stable with respect to the subsequent exposure processing or the developer and the second resist agent.

  The polystyrene-reduced weight average molecular weight Mw measured by gel permeation chromatography (GPC) of the resin having an acid dissociable group is usually 1,000 to 500,000, preferably 1,000 to 100,000, more preferably. 1,000 to 50,000. When Mw is less than 1,000, the heat resistance of the resist pattern to be formed tends to decrease. On the other hand, if the Mw exceeds 500,000, the developability tends to be lowered. Further, the ratio (Mw / Mn) of Mw of the resin having an acid dissociable group and the polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is preferably 1 to 5, More preferably, it is 1-3.

(Method for producing resin having acid dissociable group)
Resins having an acid-dissociable group include monomer components containing a polymerizable unsaturated monomer corresponding to a desired repeating unit, hydroperoxides, dialkyl peroxides, diacyl peroxides, azo compounds, etc. The radical polymerization initiator can be used and polymerized in an appropriate solvent in the presence of a chain transfer agent as necessary.

  Examples of the solvent used for polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane; cyclohexane, cycloheptane, cyclooctane, decalin, norbornane. Cycloalkanes such as benzene, toluene, xylene, ethylbenzene, cumene and other aromatic hydrocarbons; chlorobutanes, bromohexanes, dichloroethanes, halogenated hydrocarbons such as hexamethylene dibromide, chlorobenzene; ethyl acetate, Saturated carboxylic acid esters such as n-butyl acetate, i-butyl acetate and methyl propionate; ethers such as tetrahydrofuran, dimethoxyethanes and diethoxyethane; methanol, ethanol, 1-propanol, 2-propanol, 1- Butanol, 2-pig Alcohol, isobutanol, 1-pentanol, 3-pentanol, 4-methyl-2-pentanol, o-chlorophenol, 2- (1-methylpropyl) phenol, etc .; acetone, 2-butanone, Mention may be made of ketones such as 3-methyl-2-butanone, 4-methyl-2-pentanone, 2-heptanone, cyclopentanone, cyclohexanone and methylcyclohexanone. These solvents can be used alone or in combination of two or more.

  Moreover, the reaction temperature in said superposition | polymerization is 40-150 degreeC normally, Preferably it is 50-120 degreeC, and reaction time is 1-48 hours normally, Preferably it is 1-24 hours. In addition, the resin having an acid dissociable group is preferable as the content of impurities such as halogen and metal is small because sensitivity, resolution, process stability, pattern profile, and the like can be improved. Examples of purification methods for resins having acid-dissociable groups include chemical purification methods such as washing with water and liquid-liquid extraction, and combinations of these chemical purification methods with physical purification methods such as ultrafiltration and centrifugation. The method etc. can be mentioned. It is preferable that the ratio of the low molecular weight component which has a monomer as a main component contained in resin which has an acid dissociable group is 0.1 mass% or less in conversion of solid content with respect to the whole resin. The content ratio of the low molecular weight component can be measured, for example, by high performance liquid chromatography (HPLC).

(Acid generator)
The resist agent preferably contains an acid generator having a structure represented by the following general formula (2), which is decomposed by exposure. By containing an acid generator in the resist agent, an acid is generated by exposure, the acid-dissociable group is dissociated, the exposed region of the resist layer becomes alkali-soluble, and a resist pattern can be formed.

In the general formula (2), R ⁶ is a hydrogen atom, a fluorine atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched group having 1 to 10 carbon atoms. Or a linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms. R ⁴ represents a linear or branched alkyl group or alkoxyl group having 1 to 10 carbon atoms, or a linear, branched or cyclic alkanesulfonyl group having 1 to 10 carbon atoms.

In the general formula (2), R ⁵ are independently of each other a linear or branched alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group, or a substituted group. It may be a naphthyl group, or two R ⁵ may be bonded to each other to form a divalent group having 2 to 10 carbon atoms. In addition, the formed bivalent group may be substituted. k is an integer of 0 to 2, and X ⁻ is a general formula: RC _n F _2n SO ₃ ⁻ (wherein R is a fluorine atom or an optionally substituted hydrocarbon group having 1 to 12 carbon atoms. N is an integer of 1 to 10), and q is an integer of 0 to 10.

In the general formula (2), examples of the linear or branched alkyl group having 1 to 10 carbon atoms represented by R ⁴ , R ⁵ , and R ⁶ include a methyl group, an ethyl group, and n-propyl. Group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl Group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like. Of these, a methyl group, an ethyl group, an n-butyl group, a t-butyl group, and the like are preferable.

In the general formula (2), examples of the linear or branched alkoxyl group having 1 to 10 carbon atoms represented by R ⁴ and R ⁵ include a methoxy group, an ethoxy group, an n-propoxy group, i- Propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n- An octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, etc. can be mentioned. Of these, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group and the like are preferable.

In the general formula (2), examples of the linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms represented by R ⁶ include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, i -Propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, neopentyloxycarbonyl group, n-hexyloxycarbonyl group N-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group and the like. Of these, a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and the like are preferable.

In the general formula (2), examples of the linear, branched, or cyclic alkanesulfonyl group having 1 to 10 carbon atoms represented by R ⁴ include a methanesulfonyl group, an ethanesulfonyl group, and n-propanesulfonyl. Group, n-butanesulfonyl group, tert-butanesulfonyl group, n-pentanesulfonyl group, neopentanesulfonyl group, n-hexanesulfonyl group, n-heptanesulfonyl group, n-octanesulfonyl group, 2-ethylhexanesulfonyl group n -Nonanesulfonyl group, n-decanesulfonyl group, cyclopentanesulfonyl group, cyclohexanesulfonyl group, etc. can be mentioned. Of these, a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an n-butanesulfonyl group, a cyclopentanesulfonyl group, a cyclohexanesulfonyl group, and the like are preferable. Moreover, q is preferably 0-2.

In the general formula (2), examples of the optionally substituted phenyl group represented by R ⁵ include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, and 2,3-dimethylphenyl. Group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl Group, 4-ethylphenyl group, 4-t-butylphenyl group, 4-cyclohexylphenyl group, 4-fluorophenyl group and the like; linear, branched or cyclic alkyl having 1 to 10 carbon atoms A phenyl group substituted with a group; these phenyl group or alkyl-substituted phenyl group can be converted into a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxyl group, an alkoxy group; Examples include a group substituted with at least one group such as an alkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group. Examples of the alkoxyl group among the substituents for the phenyl group and the alkyl-substituted phenyl group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a 2-methylpropoxy group, 1 Examples thereof include linear, branched, or cyclic alkoxyl groups having 1 to 20 carbon atoms such as a methylpropoxy group, a t-butoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

  Examples of the alkoxyalkyl group include 2 to 21 carbon atoms such as a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group, a 2-methoxyethyl group, a 1-ethoxyethyl group, and a 2-ethoxyethyl group. And a linear, branched, or cyclic alkoxyalkyl group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, a 2-methylpropoxycarbonyl group, and a 1-methylpropoxycarbonyl group. , T-butoxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl, etc., having 2 to 21 carbon atoms, such as linear, branched, or cyclic alkoxycarbonyl groups.

Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group, t-butoxycarbonyloxy group, Examples thereof include linear, branched, or cyclic alkoxycarbonyloxy groups having 2 to 21 carbon atoms such as cyclopentyloxycarbonyl group and cyclohexyloxycarbonyl. In the general formula (2), the optionally substituted phenyl group represented by R ⁵ includes a phenyl group, a 4-cyclohexylphenyl group, a 4-t-butylphenyl group, a 4-methoxyphenyl group, a 4-t -A butoxyphenyl group and the like are preferable.

In the general formula (2), examples of the optionally substituted naphthyl group represented by R ⁵ include 1-naphthyl group, 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4 -Methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5-methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1- Naphthyl group, 2,3-dimethyl-1-naphthyl group, 2,4-dimethyl-1-naphthyl group, 2,5-dimethyl-1-naphthyl group, 2,6-dimethyl-1-naphthyl group, 2,7 -Dimethyl-1-naphthyl group, 2,8-dimethyl-1-naphthyl group, 3,4-dimethyl-1-naphthyl group, 3,5-dimethyl-1-naphthyl group, 3,6-dimethyl-1-naphthyl Group, 3,7-dimethyl-1-naphthyl group, 3, 8-dimethyl-1-naphthyl group, 4,5-dimethyl-1-naphthyl group, 5,8-dimethyl-1-naphthyl group, 4-ethyl-1-naphthyl group, 2-naphthyl group, 1-methyl-2 A naphthyl group such as a naphthyl group, a 3-methyl-2-naphthyl group or a 4-methyl-2-naphthyl group; a naphthyl substituted with a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms Group; one or more of these naphthyl groups or alkyl-substituted naphthyl groups are substituted with at least one group such as hydroxyl group, carboxyl group, cyano group, nitro group, alkoxyl group, alkoxyalkyl group, alkoxycarbonyl group, alkoxycarbonyloxy group, etc. And the like. Specific examples of the alkoxyl group, alkoxyalkyl group, alkoxycarbonyl group, and alkoxycarbonyloxy group among these substituents include the groups exemplified for the aforementioned phenyl group and alkyl-substituted phenyl group.

In the general formula (2), the optionally substituted naphthyl group represented by R ⁵ includes a 1-naphthyl group, a 1- (4-methoxynaphthyl) group, a 1- (4-ethoxynaphthyl) group, 1 -(4-n-propoxynaphthyl) group, 1- (4-n-butoxynaphthyl) group, 2- (7-methoxynaphthyl) group, 2- (7-ethoxynaphthyl) group, 2- (7-n- And propoxynaphthyl) group and 2- (7-n-butoxynaphthyl) group.

In the general formula (2), the divalent group having 2 to 10 carbon atoms formed by bonding two R ⁵ 's together with the sulfur atom in the general formula (2) is a 5-membered or 6-membered ring. Groups that form a ring, preferably a 5-membered ring (ie, a tetrahydrothiophene ring) are desirable. Examples of the substituent for the divalent group include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxyl group, an alkoxyalkyl group, an alkoxy group exemplified as the substituent for the phenyl group and the alkyl-substituted phenyl group. Examples thereof include a carbonyl group and an alkoxycarbonyloxy group. In addition, as R < ⁵ > in the said General formula (2), a methyl group, an ethyl group, a phenyl group, 4-methoxyphenyl group, 1-naphthyl group, two R < ⁵ > couple | bond together, and a tetrahydrothiophene ring structure with a sulfur atom A divalent group or the like that forms is preferable.

  Examples of the cation moiety in the general formula (2) include triphenylsulfonium cation, tri-1-naphthylsulfonium cation, tri-tert-butylphenylsulfonium cation, 4-fluorophenyl-diphenylsulfonium cation, and di-4-fluorophenyl- Phenylsulfonium cation, tri-4-fluorophenylsulfonium cation, 4-cyclohexylphenyl-diphenylsulfonium cation, 4-methanesulfonylphenyl-diphenylsulfonium cation, 4-cyclohexanesulfonyl-diphenylsulfonium cation, 1-naphthyldimethylsulfonium cation, 1- Naphthyldiethylsulfonium cation, 1- (4-hydroxynaphthyl) dimethylsulfonium cation, 1- (4 Methylnaphthyl) dimethylsulfonium cation, 1- (4-methylnaphthyl) diethylsulfonium cation, 1- (4-cyanonaphthyl) dimethylsulfonium cation, 1- (4-cyanonaphthyl) diethylsulfonium cation, 1- (3,5- Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium cation, 1- (4-methoxynaphthyl) tetrahydrothiophenium cation, 1- (4-ethoxynaphthyl) tetrahydrothiophenium cation, 1- (4-n-propoxynaphthyl) ) Tetrahydrothiophenium cation, 1- (4-n-butoxynaphthyl) tetrahydrothiophenium cation, 2- (7-methoxynaphthyl) tetrahydrothiophenium cation, 2- (7-ethoxynaphthyl) tetrahi B thiophenium cation, 2- (7-n- propoxy-naphthyl) tetrahydrothiophenium cation, 2- (7-n- butoxynaphthyl) can be exemplified tetrahydrothiophenium cation, or the like.

In the general formula (2), the “C _n F _2n —” group in the anion represented by X ⁻ (general formula: RC _n F _2n SO ³⁻ ) is a perfluoroalkylene group having n carbon atoms. However, the perfluoroalkylene group may be linear or branched. Note that n is preferably 1, 2, 4, or 8. The optionally substituted hydrocarbon group having 1 to 12 carbon atoms represented by R is preferably an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, or a bridged alicyclic hydrocarbon group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group N-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, norbornyl group, norbornylmethyl group, hydroxynorbornyl group, adamantyl group Etc.

  Preferred anion sites in the general formula (2) include trifluoromethanesulfonate anion, perfluoro-n-butanesulfonate anion, perfluoro-n-octanesulfonate anion, 2-bicyclo [2.2.1] hept-2- Yl-1,1,2,2-tetrafluoroethanesulfonate anion, 2-bicyclo [2.2.1] hept-2-yl-1,1-difluoroethanesulfonate anion, and the like.

  Said acid generator can be used individually by 1 type or in combination of 2 or more types. It is also possible to use “other acid generators” other than the above acid generators. Specific examples of “other acid generators” include onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, and sulfonic acid compounds.

  Examples of the onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like. Specific examples of the onium salt compound include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hepta-2. -Yl-1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis ( 4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2- Te La tetrafluoroethane sulfonate, cyclohexyl 2-oxo-cyclohexyl methyl trifluoromethanesulfonate, dicyclohexyl-2-oxo-cyclohexyl trifluoromethane sulfonate, and 2-oxo-cyclohexyl dimethyl sulfonium trifluoromethanesulfonate, and the like.

  Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Specific examples of halogen-containing compounds include (trichloromethyl such as phenylbis (trichloromethyl) -s-triazine, 4-methoxyphenylbis (trichloromethyl) -s-triazine, 1-naphthylbis (trichloromethyl) -s-triazine. ) -S-triazine derivatives and 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane.

  Examples of the diazoketone compound include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, a diazonaphthoquinone compound, and the like. Specific examples of the diazo ketone include 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2, naphthoquinonediazide of 2,3,4,4′-tetrahydroxybenzophenone. -4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester; 1,1,1-naphthoquinonediazide-4-sulfonic acid ester of 1,1,1-tris (4-hydroxyphenyl) ethane Examples include 2-naphthoquinonediazide-5-sulfonic acid ester.

  Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, α-diazo compounds of these compounds, and the like. Specific examples of the sulfone compound include 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, and the like.

  Examples of the sulfonic acid compounds include alkyl sulfonic acid esters, alkyl sulfonic acid imides, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Specific examples of the sulfonic acid compounds include benzoin tosylate, pyrogallol tris (trifluoromethanesulfonate), nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2.2.1] hept- 5-ene-2,3-dicarbodiimide, nonafluoro-n-butanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, perfluoro-n-octanesulfonylbicyclo [2.2 .1] Hept-5-ene-2,3-dicarbodiimide, 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarbodiimide, N- (trifluoromethanesulfonyl Xyl) succinimide, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (perfluoro-n-octanesulfonyloxy) succinimide, N- (2-bicyclo [2.2.1] hept-2-yl- 1,1,2,2-tetrafluoroethanesulfonyloxy) succinimide, 1,8-naphthalenedicarboxylic imide trifluoromethanesulfonate, 1,8-naphthalenedicarboxylic imidononafluoro-n-butanesulfonate, 1,8-naphthalenedicarboxylic Examples include acid imido perfluoro-n-octane sulfonate.

  Among these “other acid generators”, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hepta. 2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, Bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2, 2-te Lafluoroethanesulfonate, cyclohexyl, 2-oxocyclohexyl, methylsulfonium trifluoromethanesulfonate, dicyclohexyl, 2-oxocyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonylbicyclo [2.2.1] Hept-5-ene-2,3-dicarbodiimide, nonafluoro-n-butanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, perfluoro-n-octanesulfonylbicyclo [2 2.1] hept-5-ene-2,3-dicarbodiimide, 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfur Nilbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (perfluoro- n-octanesulfonyloxy) succinimide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) succinimide, 1,8-naphthalenedicarboxylic acid Imidotrifluoromethanesulfonate and the like are preferable. These “other acid generators” can be used singly or in combination of two or more.

  It is also preferred to use an acid generator having a structure represented by the general formula (2) in combination with “another acid generator”. When “other acid generator” is used in combination, the ratio of “other acid generator” used is the sum of the acid generator having the structure represented by the general formula (2) and “other acid generator”. Is usually 80% by mass or less, preferably 60% by mass or less.

  The total amount of the acid generator contained in the resist agent is 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin having an acid dissociable group from the viewpoint of ensuring the sensitivity and developability as the resist agent. It is preferable that it is 0.5 to 10 parts by mass. When the total content of the acid generator is less than 0.1 parts by mass, the sensitivity and developability of the resist agent tend to be lowered. On the other hand, if it exceeds 20 parts by mass, the transparency to radiation is lowered, and it tends to be difficult to form a rectangular resist pattern.

(solvent)
The resist agent is preferably prepared by dissolving various components including a resin having an acid dissociable group in a solvent. The solvent is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate, 2-heptanone, and cyclohexanone (hereinafter also referred to as “solvent (1)”). In addition, a solvent other than the solvent (1) (hereinafter, also referred to as “other solvent”) can be used. Furthermore, the solvent (1) and other solvents can be used in combination.

  Examples of other solvents include propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-i-propyl ether acetate, propylene glycol mono-n-butyl ether acetate, propylene glycol mono-i- Propylene glycol monoalkyl ether acetates such as butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, propylene glycol mono-t-butyl ether acetate; 2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, Linear or 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-octanone, etc. Branched ketones;

  Cyclic ketones such as cyclopentanone, 3-methylcyclopentanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, isophorone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxypropionic acid n-propyl, i-propyl 2-hydroxypropionate, n-butyl 2-hydroxypropionate, i-butyl 2-hydroxypropionate, sec-butyl 2-hydroxypropionate, t-butyl 2-hydroxypropionate, etc. Alkyl 2-hydroxypropionates; in addition to alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate,

  n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, propylene glycol monomethyl ether , Propylene glycol monoethyl Ether, propylene glycol mono-n-propyl ether, toluene, xylene, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoacetate, Ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol Cole monoethyl ether, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, etc. Can do.

  Of these solvents, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, alkyl 2-hydroxypropionate, alkyl 3-alkoxypropionate, γ-butyrolactone and the like are preferable. . These solvents can be used singly or in combination of two or more.

  When the solvent (1) and another solvent are used in combination as the solvent, the proportion of the other solvent is usually 50% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less, based on the total amount of the solvent. It is. The amount of the solvent contained in the resist agent is such that the concentration of the total solid contained in the resist agent is usually 2 to 70% by mass, preferably 4 to 25% by mass, and more preferably 4 to 10% by mass. Is the amount.

  The resist agent is prepared by dissolving each component in a solvent so that the total solid content concentration is in the above-described numerical range to obtain a uniform solution, and then filtering with a filter having a pore size of about 0.02 μm, for example. be able to.

(Acid diffusion control agent)
The resist agent preferably contains an acid diffusion control agent. The acid diffusion control agent is a component having an action of controlling a diffusion phenomenon of an acid generated from an acid generator by exposure in a resist layer and suppressing an undesirable chemical reaction in a non-exposed region. By blending such an acid diffusion control agent, the storage stability of the resist agent is improved, the resolution of the resist is further improved, and due to fluctuations in the holding time (PED) from exposure to heat treatment after exposure. A change in the line width of the resist pattern can be suppressed, and a composition having extremely excellent process stability can be obtained. As the acid diffusion controller, it is preferable to use a nitrogen-containing organic compound or a photodisintegratable base. This photodegradable base is an onium salt compound that is decomposed by exposure and loses acid diffusion controllability.

(Nitrogen-containing organic compounds)
Examples of the nitrogen-containing organic compound include a compound represented by the following general formula (3) (hereinafter, also referred to as “nitrogen-containing compound (I)”), a compound having two nitrogen atoms in the same molecule (hereinafter, “ Nitrogen-containing compound (II) ”, polyamino compounds having three or more nitrogen atoms in the same molecule and polymers thereof (hereinafter collectively referred to as“ nitrogen-containing compound (III) ”), amide group-containing compounds , Urea compounds, nitrogen-containing heterocyclic compounds, and the like.

In the general formula (3), R ⁷ independently of each other represents a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or non-substituted group. A substituted aralkyl group is shown.

  Examples of the nitrogen-containing compound (I) include mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine; di-n- Butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine, etc. Di (cyclo) alkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine , Tri-n-nonylamine, tri-n-decylamine, cyclohexyl Tri (cyclo) alkylamines such as dimethylamine, methyldicyclohexylamine and tricyclohexylamine; substituted alkylamines such as 2,2 ′, 2 ″ -nitrotriethanol; aniline, N-methylaniline, N, N-dimethylaniline 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine, 2,4,6-tri-tert-butyl-N-methylaniline, N-phenyldiethanolamine Aromatic amines such as 2,6-diisopropylaniline are preferred.

  Examples of the nitrogen-containing compound (II) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, and 4,4′-diaminodiphenylether. 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2, -(4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) ) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methyl ester Benzene], bis (2-dimethylaminoethyl) ether, bis (2-diethylaminoethyl) ether, 1- (2-hydroxyethyl) -2-imidazolidinone, 2-quinoxalinol, N, N, N ′ , N′-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine and the like are preferable.

  As the nitrogen-containing compound (III), for example, polyethyleneimine, polyallylamine, 2-dimethylaminoethylacrylamide polymer and the like are preferable.

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

  Examples of urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butylthiourea. Etc. are preferred. Examples of the nitrogen-containing heterocyclic compound include imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2- Imidazoles such as methyl-1H-imidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine , Nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine, pyridines such as 2,2 ′: 6 ′, 2 ″ -terpyridine; piperazine, 1- (2-hydroxyethyl ) In addition to piperazines such as piperazine, Gin, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, piperidine ethanol, 3-piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetylmorpholine, 3 -(N-morpholino) -1,2-propanediol, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane and the like are preferable.

(Photodegradable base)
A photodegradable base is an onium salt compound that generates a base that decomposes upon exposure and exhibits acid diffusion controllability. Specific examples of such an onium salt compound include a sulfonium salt compound represented by the following general formula (4) and an iodonium salt compound represented by the following general formula (5).

In said general formula (4) and (5), R < ⁸ > -R < ¹² > shows a hydrogen atom, an alkyl group, an alkoxyl group, a hydroxyl group, or a halogen atom mutually independently. Z ⁻ represents OH ⁻ , R—COO ⁻ , R—SO ₃ ^— (wherein R represents an alkyl group, an aryl group, or an alkaryl group), or an anion represented by the following formula (6). Show.

  Specific examples of the sulfonium salt compound and the iodonium salt compound include triphenylsulfonium hydroxide, triphenylsulfonium acetate, triphenylsulfonium salicylate, diphenyl-4-hydroxyphenylsulfonium hydroxide, diphenyl-4-hydroxyphenylsulfonium acetate, Diphenyl-4-hydroxyphenylsulfonium salicylate, bis (4-t-butylphenyl) iodonium hydroxide, bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium hydroxide, bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium salicylate, 4-t-butyl Enyl-4-hydroxyphenyliodonium hydroxide, 4-t-butylphenyl-4-hydroxyphenyliodonium acetate, 4-t-butylphenyl-4-hydroxyphenyliodonium salicylate, bis (4-t-butylphenyl) iodonium Examples thereof include 10-camphor sulfonate, diphenyliodonium 10-camphor sulfonate, triphenylsulfonium 10-camphor sulfonate, and 4-t-butoxyphenyl diphenylsulfonium 10-camphor sulfonate.

  The above acid diffusion control agents can be used singly or in combination of two or more. The compounding amount of the acid diffusion controller is usually 15 parts by mass or less, preferably 10 parts by mass or less, and more preferably 5 parts by mass or less with respect to 100 parts by mass of the resin having an acid dissociable group. If the compounding amount of the acid diffusion controller is more than 15 parts by mass, the sensitivity of the resist agent tends to decrease. If the amount of the acid diffusion control agent is less than 0.001 part by mass, the shape and dimensional fidelity of the resist pattern may be lowered depending on the process conditions.

(Additive)
Various additives such as a surfactant, a sensitizer, and an aliphatic additive can be blended with the resist agent as necessary.

  A surfactant is a component that exhibits an effect of improving coating properties, striation, developability, and the like. Examples of such surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, and polyethylene glycol dilaurate. Nonionic surfactants such as polyethylene glycol distearate; hereinafter referred to as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (above, manufactured by Kyoeisha Chemical Co., Ltd.), F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), Megafax F171, F173 (above, manufactured by Dainippon Ink and Chemicals), Florard FC430, FC431 (above, manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 ( As mentioned above, Asahi Glass Co., Ltd.) can be mentioned. These surfactants can be used singly or in combination of two or more. The compounding quantity of surfactant is normally 2 mass parts or less with respect to 100 mass parts of hydroxyl-containing resin.

  The sensitizer absorbs radiation energy and transmits the energy to the acid generator, thereby increasing the amount of acid generated, and has the effect of improving the apparent sensitivity of the resist agent. Have. Examples of such sensitizers include carbazoles, acetophenones, benzophenones, naphthalenes, phenols, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines, and the like. These sensitizers can be used individually by 1 type or in combination of 2 or more types. Further, by blending a dye or a pigment, the latent image in the exposed area can be visualized, and the influence of halation during exposure can be reduced. Furthermore, adhesiveness with a board | substrate can be improved by mix | blending an adhesion aid. The compounding quantity of a sensitizer is 50 mass parts or less normally with respect to 100 mass parts of hydroxyl-containing resin.

  Examples of the alicyclic additive that can be added to the resist agent include an alicyclic additive having an acid dissociable group and an alicyclic additive having no acid dissociable group. Such an alicyclic additive is a component having an effect of further improving dry etching resistance, pattern shape, adhesion to a substrate, and the like. Specific examples of the alicyclic additive include 1-adamantanecarboxylic acid, 2-adamantanone, 1-adamantanecarboxylic acid t-butyl, 1-adamantanecarboxylic acid t-butoxycarbonylmethyl, 1-adamantanecarboxylic acid α-butyrolactone Ester, 1,3-adamantane dicarboxylate di-t-butyl, 1-adamantane acetate t-butyl, 1-adamantane acetate t-butoxycarbonylmethyl, 1,3-adamantane diacetate di-t-butyl, 2,5- Adamantane derivatives such as dimethyl-2,5-di (adamantylcarbonyloxy) hexane; deoxycholic acid t-butyl, deoxycholic acid t-butoxycarbonylmethyl, deoxycholic acid 2-ethoxyethyl, deoxycholic acid 2-cyclohexyloxy Ethyl, deoxycholic acid -Deoxycholic acid esters such as oxocyclohexyl, deoxycholic acid tetrahydropyranyl, deoxycholic acid mevalonolactone ester; lithocholic acid t-butyl, lithocholic acid t-butoxycarbonylmethyl, lithocholic acid 2-ethoxyethyl, lithocholic acid 2 -Lithocholic acid esters such as cyclohexyloxyethyl, lithocholic acid 3-oxocyclohexyl, lithocholic acid tetrahydropyranyl, lithocholic acid mevalonolactone ester; dimethyl adipate, diethyl adipate, dipropyl adipate, di-n-butyl adipate, Alkyl carboxylic acid esters such as di-t-butyl adipate; 3- [2-hydroxy-2,2-bis (trifluoromethyl) ethyl] tetracyclo [4.4.0.12,5.17,10] A dodecane etc. can be mentioned.

  These alicyclic additives can be used singly or in combination of two or more. The compounding quantity of an alicyclic additive is 50 mass parts or less normally with respect to 100 mass parts of hydroxyl-containing resin, Preferably it is 30 mass parts or less. When the blending amount of the alicyclic additive is more than 50 parts by mass with respect to 100 parts by mass of the hydroxyl group-containing resin, the heat resistance as a resist tends to decrease. Furthermore, examples of additives other than the above include alkali-soluble resins, low-molecular alkali solubility control agents having an acid-dissociable protecting group, antihalation agents, storage stabilizers, antifoaming agents, and the like.

3. Resist pattern insolubilized resin composition:
The resist pattern insolubilized resin composition is used for making the first resist pattern an insolubilized resist pattern in the resist pattern forming method described above. This insolubilized resin composition usually contains a resin having a hydroxyl group and an alcohol solvent.

(Resin having a hydroxyl group)
Resin having a hydroxyl group (hereinafter also referred to as “hydroxyl group-containing resin”) is a monomer component containing at least one of hydroxyacrylanilide and hydroxymethacrylanilide (hereinafter also simply referred to as “hydroxy (meth) acrylanilide”). A resin obtained by polymerization is preferred.

(Hydroxy (meth) acrylanilide)
Examples of the hydroxy (meth) acrylic anilide, may be mentioned compounds represented by the general formula (7).

Among the groups represented by R ¹⁴ in the general formula (7), specific examples of the linear, branched or cyclic divalent hydrocarbon group include a methylene group, an ethylene group, a propylene group (1, 3-propylene group, 1,2-propylene group), tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, trideca Methylene group, tetradecamethylene group, pentadecamethylene group, hexadecamethylene group, heptacamethylene group, octadecamethylene group, nonacamethylene group, icosalen group, 1-methyl-1,3-propylene group, 2-methyl -1,3-propylene group, 2-methyl-1,2-propylene group, 1-methyl-1,4-butylene group, 2-methyl-1,4- Saturated chain hydrocarbon groups such as butylene, ethylidene, 1-propylidene and 2-propylidene; cyclobutylene such as 1,3-cyclobutylene and cyclopentylene such as 1,3-cyclopentylene A monocyclic hydrocarbon ring such as a cycloalkylene group having 3 to 10 carbon atoms such as a cyclohexylene group such as a 1,4-cyclohexylene group and a cyclooctylene group such as a 1,5-cyclooctylene group Groups: 2-4 cyclic groups including norbornylene groups such as 1,4-norbornylene group and 2,5-norbornylene group, adamantylene groups such as 1,5-adamantylene group and 2,6-adamantylene group Examples thereof include a bridged cyclic hydrocarbon ring group such as a hydrocarbon ring group having 4 to 30 carbon atoms. In addition, as a monomer (hydroxy (meth) acrylanilide) represented by the said General formula (7), p-hydroxymethacrylanilide is preferable. The proportion of hydroxy (meth) acrylanilide used is usually 30 to 95 mol%, preferably 40 to 90 mol%, based on 100 mol% of the monomer component.

(Monomer (1))
The monomer component used for producing a hydroxyl group-containing resin, at least a monomer represented by the monomer in the general formula represented by the general formula (8-1) (8-2) Any one (hereinafter also referred to as “monomer (1)”) is preferably further included.

  Specific examples of the monomer (1) include glycidyl methacrylate, glycidyl acrylate, (1-ethyl-1-oxetanyl) methyl methacrylate (manufactured by Ube Industries, trade name “OXMA”), 2-[(3,5- Dimethylpyrazolyl) carbonylamino] ethyl methacrylate (Showa Denko, trade name “MOI-BP”), 2- [0- (1-methylpropylideneamino) carbonylamino] ethyl methacrylate (Showa Denko, trade name “ MOI-BM ") and the like.

  The proportion of the monomer (1) used is usually 5 to 60 mol%, preferably 5 to 50 mol%, more preferably 5 to 40 mol% with respect to 100 mol% of the monomer component.

(Monomer (2))
It is preferable that the monomer component used for producing the hydroxyl group-containing resin further includes a monomer (monomer (2)) represented by the following general formula (10).

In the general formula (10), R ¹⁹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxyl group having 1 to 8 carbon atoms. R ¹⁹ in the general formula (10) is preferably a tert-butyl group, an acetoxy group, or a 1-ethoxyethoxy group, and more preferably a tert-butyl group.

  The monomer (2) is a so-called styrene derivative. This monomer (2) is preferably a monomer having a specific functional group that can be converted into a phenolic hydroxyl group after copolymerization. Specific examples thereof include p-acetoxystyrene, α-methyl-p- Acetoxystyrene, p-benzyloxystyrene, p-tert-butoxystyrene, p-tert-butoxycarbonyloxystyrene, p-tert-butyldimethylsiloxystyrene and the like can be mentioned. In addition, if a monomer having such a specific functional group is copolymerized and then subjected to an appropriate treatment such as hydrolysis using hydrochloric acid or the like, the specific functional group can be easily converted into a phenolic hydroxyl group. can do.

  The proportion of the monomer (2) used is usually 5 to 65 mol%, preferably 10 to 50 mol%, relative to 100 mol% of the monomer component.

(Other monomers)
The monomer component used for producing the hydroxyl group-containing resin includes a monomer having an alcoholic hydroxyl group (monomer (3)), a monomer having a hydroxyl group derived from an organic acid such as a carboxylic acid (single monomer). A monomer (4)) and at least one monomer selected from the group consisting of monomers having a phenolic hydroxyl group (monomer (5)) (other monomers) may be further included. preferable. However, the monomer (5) does not include hydroxy (meth) acrylanilide.

  Specific examples of the monomer (3) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, glycerol mono Examples thereof include hydroxyalkyl (meth) acrylates such as methacrylate. Of these, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferable. In addition, these monomers (4) can be used individually by 1 type or in combination of 2 or more types.

  The proportion of the monomer (3) used is usually 5 to 65 mol%, preferably 10 to 60 mol%, relative to 100 mol% of the monomer component.

  Specific examples of the monomer (4) include acrylic acid, methacrylic acid, crotonic acid, 2-succinoloylethyl (meth) acrylate, 2-malenoylethyl (meth) acrylate, and 2-hexahydrophthaloylethyl. Monocarboxylic acids such as (meth) acrylate, ω-carboxy-polycaprolactone monoacrylate, monohydroxyethyl phthalate, acrylic acid dimer, 2-hydroxy-3-phenoxypropyl acrylate, t-butoxy methacrylate, t-butyl acrylate; Examples thereof include (meth) acrylic acid derivatives having a carboxyl group, including dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid. Of these, acrylic acid, methacrylic acid, and 2-hexahydrophthaloylethyl methacrylate are preferable. In addition, these monomers (4) can be used individually by 1 type or in combination of 2 or more types.

  The proportion of the monomer (4) used is usually 5 to 65 mol%, preferably 10 to 60 mol%, relative to 100 mol% of the monomer component. An example of a commercial product of ω-carboxy-polycaprolactone monoacrylate is “Aronix M-5300” manufactured by Toagosei Co., Ltd. Moreover, as a commercial item of an acrylic acid dimer, there exists a brand name "Aronix M-5600" by Toagosei Co., Ltd., for example. Furthermore, as a commercial item of 2-hydroxy-3-phenoxypropyl acrylate, there is a trade name “Aronix M-5700” manufactured by Toagosei Co., Ltd., for example.

  Specific examples of the monomer (5) include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, α-methyl-p-hydroxystyrene, α-methyl-m-hydroxystyrene, α-methyl-o. -Hydroxystyrene, 2-allylphenol, 4-allylphenol, 2-allyl-6-methylphenol, 2-allyl-6-methoxyphenol, 4-allyl-2-methoxyphenol, 4-allyl-2,6-dimethoxy Phenol, 4-allyloxy-2-hydroxybenzophenone, etc. can be mentioned. Of these, p-hydroxystyrene and α-methyl-p-hydroxystyrene are preferable.

  The proportion of the monomer (5) used is usually 5 to 65 mol%, preferably 5 to 50 mol%, more preferably 5 to 45 mol% with respect to 100 mol% of the monomer component.

  The use ratio of the above-mentioned “other monomers” is usually in the above-mentioned range. If the ratio of the “other monomer” used is too small, there are too few reactive sites that react with the crosslinking component described later, so that there is a tendency that the resist pattern is less likely to shrink. On the other hand, if the ratio of the “other monomer” used is too large, the resist pattern may be buried due to swelling during development. That is, if the usage ratio of “other monomer” is outside the above-described range, it may be difficult to control the line width variation of the insolubilized resist pattern formed using the insolubilized resin composition.

(And other monomers)
It is preferable that the monomer component used for producing the hydroxyl group-containing resin further includes “another monomer” for the purpose of controlling the hydrophilicity and solubility of the resulting hydroxyl group-containing resin. Specific examples of “further monomers” include (meth) acrylic acid aryl esters, dicarboxylic acid diesters, nitrile group-containing polymerizable compounds, amide bond-containing polymerizable compounds, vinyls, allyls, and chlorine-containing compounds. Examples thereof include a polymerizable compound and a conjugated diolefin. Further specific examples include dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; (meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate; t-butyl (meta ) (Meth) acrylic esters such as acrylate, 4,4,4-trifluoro-3-hydroxy-1-methyl-3-trifluoromethyl-1-butyl (meth) acrylate; nitriles such as acrylonitrile and methacrylonitrile Group-containing polymerizable compounds; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide; fatty acid vinyls such as vinyl acetate; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; 1,3-butadiene, isoprene, 1, Conjugated geology such as 4-dimethylbutadiene Mention may be made of a kind. These “further monomers” can be used singly or in combination of two or more.

  Preferable examples of “further monomers” include compounds represented by the following general formula (11).

In the general formula (11), R ^{20 to} R ²² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxymethyl group, a trifluoromethyl group, or a phenyl group, and R ²³ represents Represents a monovalent organic group, R ²⁴ represents a single bond or a divalent organic group having 1 to 20 carbon atoms, and B represents a single bond, an oxygen atom, a carbonyl group, a carbonyloxy group, or an oxycarbonyl. Indicates a group.

In the general formula (11), among the groups represented by R ^{20 to} R ²² , specific examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, A hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc. can be mentioned. In the general formula (11), R ²⁰ and R ²¹ are preferably hydrogen atoms, and R ²² is preferably a hydrogen atom or a methyl group.

In the general formula (11), the monovalent organic group represented by R ²³ is preferably a monovalent organic group containing a fluorine atom, and more preferably a fluoroalkyl group having 1 to 20 carbon atoms. A fluoroalkyl group having 1 to 4 carbon atoms is particularly preferable.

  Specific examples of the fluoroalkyl group having 1 to 20 carbon atoms include a difluoromethyl group, a perfluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, and a 2,2,2-trifluoroethyl group. Perfluoroethyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl)- 1,2,2,2-tetrafluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 1, 1,2,2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1-bis (trifluoro) methyl-2,2,2-trifluoroethyl group, 2- (perf) Olopropyl) ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group, perfluoropentyl group, 1,1,2,2,3,3,4,4,5,5 -Decafluoropentyl group, 1,1-bis (trifluoromethyl) -2,2,3,3,3-pentafluoropropyl group, perfluoropentyl group, 2- (perfluorobutyl) ethyl group, 1,1 , 2,2,3,3,4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl group Perfluoropentylmethyl group, perfluorohexyl group, 2- (perfluoropentyl) ethyl group, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoroheptyl group , Perfluorohexylmethyl group, perfluoroheptyl Group, 2- (perfluorohexyl) ethyl group, 1,1,2,2,3,3,4,4,5,5,6,6,7,7-tetradecafluorooctyl group, perfluoroheptylmethyl Group, perfluorooctyl group, 2- (perfluoroheptyl) ethyl group, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexa Decafluorononyl group, perfluorooctylmethyl group, perfluorononyl group, 2- (perfluorooctyl) ethyl group, 1,1,2,2,3,3,4,4,5,5,6,6 7,7,8,8,9,9-octadecafluorodecyl group, perfluorononylmethyl group, perfluorodecyl group and the like can be mentioned.

  When the number of carbon atoms of the fluoroalkyl group is too large, the solubility of the resulting hydroxyl group-containing resin in an alkaline aqueous solution tends to be low. Therefore, a perfluoromethyl group, a perfluoroethyl group, or a perfluoropropyl group is preferable.

Specific examples of the divalent organic group having 1 to 20 carbon atoms among the groups represented by R ²⁴ in the general formula (11) include a methylene group, an ethylene group, and a propylene group (1,3-propylene group). 1,2-propylene group), tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetra Decamethylene group, pentadecamethylene group, hexadecamethylene group, heptacamethylene group, octadecamethylene group, nonadecamethylene group, insalen group, 1-methyl-1,3-propylene group, 2-methyl-1,3 -Propylene group, 2-methyl-1,2-propylene group, 1-methyl-1,4-butylene group, 2-methyl-1,4-butylene group Saturated chain hydrocarbon groups such as methylidene group, ethylidene group, 1-propylidene group and 2-propylidene group; cyclobutylene groups such as 1,3-cyclobutylene group and cyclopentylene groups such as 1,3-cyclopentylene group Monocyclic carbonization of cycloalkylene groups having 3 to 10 carbon atoms, including cyclohexylene groups such as lenylene groups, 1,4-cyclohexylene groups, and cyclooctylene groups such as 1,5-cyclooctylene groups A hydrogen ring group; a norbornylene group such as a 1,4-norbornylene group or a 2,5-norbornylene group; an adamantylene group such as a 1,5-adamantylene group or a 2,6-adamantylene group; Examples thereof include a bridged cyclic hydrocarbon ring group such as a hydrocarbon ring group having 4 to 20 cyclic carbon atoms.

  Preferable examples of the “further monomer” represented by the general formula (11) include 2-(((trifluoromethyl) sulfonyl) amino) ethyl-1-methacrylate, 2-(((trifluoro Examples include methyl) sulfonyl) amino) ethyl-1-acrylate, compounds represented by formulas (11-1) to (11-6), and the like.

  The usage ratio of “further monomer” is usually 1 to 50 mol%, preferably 2 to 30 mol%, more preferably 2 to 20 mol%, relative to 100 mol% of the monomer component. .

(Method for producing hydroxyl group-containing resin)
Hydroxyl group-containing resins, for example, use monomer components, radical polymerization initiators such as hydroperoxides, dialkyl peroxides, diacyl peroxides, azo compounds, etc., if necessary in the presence of a chain transfer agent. Can be produced by polymerization in an appropriate solvent. Examples of the solvent used for polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane; cyclohexane, cycloheptane, cyclooctane, decalin, norbornane. Cycloalkanes such as benzene, toluene, xylene, ethylbenzene, cumene and other aromatic hydrocarbons; chlorobutanes, bromohexanes, dichloroethanes, halogenated hydrocarbons such as hexamethylene dibromide, chlorobenzene; ethyl acetate, Saturated carboxylic acid esters such as n-butyl acetate, i-butyl acetate, methyl propionate, and propylene glycol monomethyl ether acetate; alkyl lactones such as γ-butyrolactone; and amines such as tetrahydrofuran, dimethoxyethanes, diethoxyethanes, etc. Alkyls such as 2-butanone, 2-heptanone and methyl isobutyl ketone; cycloalkyl ketones such as cyclohexanone; 2-propanol, 1-butanol, 4-methyl-2-pentanol, propylene glycol monomethyl ether, etc. And the like. These solvents can be used alone or in combination of two or more.

  The reaction temperature in the polymerization is usually 40 to 120 ° C., preferably 50 to 100 ° C., and the reaction time is usually 1 to 48 hours, preferably 1 to 24 hours.

  The purity of the hydroxyl group-containing resin is preferably high, and not only the content of impurities such as halogen and metal is low, but the residual monomer and oligomer components are not more than predetermined values, for example, 0.1% by mass or less by HPLC analysis. It is preferable that When an insolubilized resin composition containing a high-purity hydroxyl group-containing resin is used, process stability can be improved and the resist pattern shape can be further refined. Examples of the method for purifying the hydroxyl group-containing resin include the following methods. As a method for removing impurities such as metals, a method in which a metal in a polymerization solution is adsorbed using a zeta potential filter, a metal is chelated and removed by washing the polymerization solution with an acidic aqueous solution such as oxalic acid or sulfonic acid. And the like. In addition, as a method of making the residual ratio of the monomer and oligomer components below the specified value, a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water washing and an appropriate solvent, a specific molecular weight or less Refining method to remove residual monomers by coagulating resin in poor solvent by dripping polymerization solution into poor solvent And a purification method in a solid state such as washing with a poor solvent for the resin slurry separated by filtration. Note that these methods may be combined.

  The weight-average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the hydroxyl group-containing resin thus obtained is usually 1,000 to 500,000, preferably 1,000 to 50, 000, more preferably 1,000 to 20,000. If the weight average molecular weight (Mw) is more than 500,000, it tends to be difficult to remove with a developer after heat curing. On the other hand, when the weight average molecular weight (Mw) is less than 1,000, it tends to be difficult to form a uniform coating film after coating.

(Alcohol solvent)
The alcohol solvent contains alcohol. This alcohol solvent should be used as long as it can sufficiently dissolve the hydroxyl group-containing resin and the crosslinking component contained as necessary and does not dissolve the first resist pattern formed with the first resist agent. Can do. As the alcohol contained in the alcohol solvent having such properties, a monohydric alcohol having 1 to 8 carbon atoms is preferable. More specifically, 1-propanol, isopropanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl -1-butanol, 3-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pen Tanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 1-heptanol 2-heptanol, 2-methyl-2-heptanol, 2-methyl-3-heptanol and the like. Of these, 1-butanol, 2-butanol, and 4-methyl-2-pentanol are preferable. These alcohols can be used singly or in combination of two or more.

  The water content of the alcohol solvent (water content relative to the total solvent) is preferably 10% by mass or less, and more preferably 3% by mass or less. When the water content of the alcohol solvent exceeds 10% by mass, the solubility of the hydroxyl group-containing resin tends to decrease. The alcohol solvent is particularly preferably a non-aqueous solvent containing alcohol (an anhydrous alcohol solvent substantially free of water).

(Other solvents)
The insolubilized resin composition may contain “other solvents” other than the alcohol solvent described above for the purpose of adjusting the coating property when applied onto the first resist pattern. As the “other solvent”, a solvent that does not erode the first resist pattern and that uniformly applies the insolubilized resin composition can be used.

  Specific examples of “other solvents” include cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Alkyl ethers of polyhydric alcohols such as dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; ethylene glycol ethyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol ethyl ether Alkyl ether acetates of polyhydric alcohols such as teracetate and propylene glycol monomethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2- Ketones such as pentanone and diacetone alcohol; ethyl acetate, butyl acetate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, hydroxy Ethyl acetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate An ester such as ethyl acetate or butyl acetate, and water or the like. Of these, cyclic ethers, polyhydric alcohol alkyl ethers, polyhydric alcohol alkyl ether acetates ketones, esters, and water are preferred.

  The blending ratio of “other solvent” is usually 30% by mass or less, preferably 20% by mass or less, with respect to the total solvent. If the blending ratio of “other solvent” exceeds 30% by mass, the first resist pattern may be eroded and problems such as intermixing with the insolubilized resin composition may occur. One resist pattern may be buried. In addition, when mix | blending water as "another solvent", it is preferable that the mixture ratio is 10 mass% or less.

(Crosslinking component)
The insolubilized resin composition preferably contains a crosslinking component as an optional component. The crosslinking component is a component that exhibits an action of curing the hydroxyl group-containing resin by reacting with the hydroxyl group-containing resin or the crosslinking components by the action of an acid.

  The crosslinking component is a compound having a group represented by the following general formula (12) (hereinafter also referred to as “crosslinking component I”) or a compound having two or more cyclic ethers as a reactive group (hereinafter referred to as “crosslinking component II”). "). The crosslinking component preferably includes both the crosslinking component I and the crosslinking component II.

In the general formula (12), R ²⁵ and R ²⁶ represent a hydrogen atom or a group represented by the following general formula (13). However, at least one of R ²⁵ and R ²⁶ is a group represented by the following formula (13).

In the general formula (13), R ²⁷ and R ²⁸ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 1 to 6 carbon atoms, or a carbon number 2 in which R ²⁷ and R ²⁷ are connected to each other. -10 represents a ring of 10 to 10, and R ²⁹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. This crosslinking component exhibits an action of curing the hydroxyl group-containing resin by reacting with the hydroxyl group-containing resin or between the crosslinking components by the action of an acid.

  Specific examples of the crosslinking component I include compounds having a functional group such as an imino group, a methylol group, or a methoxymethyl group in the molecule. More specifically, alkylation is performed by alkylating all or part of active methylol groups such as (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, (poly) methylolated urea, etc. A nitrogen-containing compound as ether can be mentioned. Examples of the alkyl group include a methyl group, an ethyl group, a butyl group, or a mixture thereof. The nitrogen-containing compound may contain an oligomer component partially self-condensed. Specific examples of the nitrogen-containing compound include hexamethoxymethylated melamine, hexabutoxymethylated melamine, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril and the like.

Of the specific examples of the crosslinking component I, commercially available compounds include the following trade names: Cymel 300, 301, 303, 350, 232, 235, 236, 238, 266, 267, 285, 1123, 1123-10, 1170, 370, 771, 772, 172, 1172, 325, 327, 703, 712, 254, 253, 212, 1128, 701, 202, 207 (Nippon Cytec Co., Ltd.), Nicarak MW-30M, 30, 22, 24X, Nicarak MS-21, 11, 001, Nicarax MX-002, 730, 750, 708, 708, 706, 042, 035, 45, 410, 302, 202, Nicarak SM-651, 652, 653 551, 451, Nicarak SB-401, 355, 303, 301, 255, 203, 201, Nicarax BX-4000, 37, 55H, Nicarac BL-60 (Sanwa Chemical) For example). Among them, Cymel 325, 327, 703, 712, 254, R ¹ and R ^{2 in} the general formula (1) correspond to a compound containing a hydrogen atom, that is, an imino group. 253, 212, 1128, 701, 202, and 207 are preferable.

  Specific examples of the crosslinking component II include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy). Cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4 ′ -Epoxy-6'-methylcyclohexanecarboxylate, methylene bis (3,4-epoxycyclohexane), di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis (3,4-epoxycyclohexanecarboxylate), epsilon -Caprolactone modification , 4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3 An epoxycyclohexyl group-containing compound such as 1,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate;

  Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, Hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol Diglycidyl ether, polypropylene glycol diglycidyl ethers, ethylene glycol, propylene group Call, polyglycidyl ethers of polyether polyols obtained by adding an aliphatic polyhydric one or more alkylene oxides to an alcohol such as glycerin; diglycidyl esters of aliphatic long chain dibasic acid;

  Monoglycidyl ethers of aliphatic higher alcohols; monoglycidyl ethers of polyether alcohols obtained by adding phenol, cresol, butylphenol, or alkylene oxide thereto; glycidyl esters of higher fatty acids;

  3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1,3- (2-methylenyl) propanediylbis (oxymethylene)) bis- (3-ethyloxetane), 1 , 4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl- 3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethyleneglycolbis (3-ethyl-3 -Oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, Licyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol Bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, di Ntaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ) Ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis (3 -Ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3- Examples thereof include oxetane compounds having two or more oxetane rings in the molecule, such as ethyl-3-oxetanylmethyl) ether and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether.

  Among these, 1,6-hexanediol diglycidyl ether and dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether are preferable as the crosslinking component II. These crosslinking components can be used singly or in combination of two or more. In addition, among the specific examples of the crosslinking component II, the commercially available compounds are the following trade names: Aron Oxetane OXT-101, 121, 221 (above, manufactured by Toagosei Co., Ltd.), OXTP, OXBP (above. And Ube Industries, Ltd.).

  The amount of the crosslinking component contained in the insolubilized resin composition is preferably 1 to 100 parts by mass and more preferably 5 to 70 parts by mass with respect to 100 parts by mass of the hydroxyl group-containing resin. If it is less than 1 part by mass, curing will be insufficient and the resist pattern will tend not to shrink. On the other hand, if it exceeds 100 parts by mass, curing may proceed excessively and the resist pattern may be buried.

  Moreover, it is preferable that the total content rate of hydroxyl-containing resin and a crosslinking component is 0.1-30 mass% with respect to the whole insolubilization resin composition containing a non-aqueous solvent and alcohol solvent, and 1-20. More preferably, it is mass%. When the total content ratio of the hydroxyl group-containing resin and the crosslinking component is less than 0.1% by mass, the coating film becomes too thin, and the pattern edge portion may be cut off. On the other hand, if it exceeds 30% by mass, the viscosity becomes too high, and it may be difficult to embed in a fine pattern.

(Surfactant)
A surfactant may be added to the insolubilized resin composition for the purpose of improving the coating property, antifoaming property, leveling property and the like of the insolubilized resin composition. Specific examples of surfactants that can be blended are as follows: BM-1000, BM-1100 (above, manufactured by BM Chemie); MegaFuck F142D, F172, F173, F183 (above, large) Nippon Ink Chemical Co., Ltd.); Fluorad FC-135, FC-170C, FC-430, FC-431 (above, manufactured by Sumitomo 3M); Surflon S-112, S-113, S-131, Fluorine series such as S-141, S-145 (made by Asahi Glass Co., Ltd.); SH-28PA, -190, -193, SZ-6032, SF-8428 (made by Toray Dow Corning Silicone Co., Ltd.) Mention may be made of surfactants. In addition, the compounding quantity of these surfactants becomes like this. Preferably it is 5 mass parts or less with respect to 100 mass parts of hydroxyl-containing resin.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. Moreover, the measuring method of various physical-property values and the evaluation method of various characteristics are shown below.

  [Mw and Mn]: Using a GPC column manufactured by Tosoh Corporation (trade name “G2000HXL”, trade name “G3000HXL”, trade name “G4000HXL”), flow rate: 1.0 mL / min, elution Measurement was performed by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis conditions of solvent: tetrahydrofuran, column temperature: 40 ° C. Further, the degree of dispersion “Mw / Mn” was calculated from the measurement results of Mw and Mn.

  [Remaining ratio of low molecular weight components]: Using a trade name “Inertsil ODS-25 μm column” (4.6 mmφ × 250 mm) manufactured by GL Sciences, flow rate: 1.0 mL / min, elution solvent: acrylonitrile / 0.1 It was measured by high performance liquid chromatography (HPLC) under the analysis conditions of a% phosphoric acid aqueous solution. The low molecular weight component is a component having a monomer as a main component, more specifically, a component having a molecular weight of less than 1,000, preferably a component having a molecular weight of or less than that of the trimer.

[ ¹³ C-NMR analysis]: The product name “JNM-EX270” manufactured by JEOL Ltd. was used, and CDCl ₃ was used as a measurement solvent.

  [Evaluation of Pattern]: Using a scanning electron microscope (trade name “S-9380”, manufactured by Hitachi Keiki Co., Ltd.), the resist patterns formed on the evaluation substrates B and C were evaluated according to the following criteria.

<Evaluation board B>
The case where the first resist pattern remained was evaluated as “◯”, and the case where the first resist pattern disappeared was evaluated as “x”.

<Evaluation substrate C>
A case where a 50 nm line / 200 nm pitch line and space pattern is additionally formed between the insolubilized resist patterns formed on the evaluation substrate B is evaluated as “◯”, and the case where the insolubilized resist pattern disappears is indicated as “×”. ".

(Synthesis Example 1: Resin (A-1))
50.16 g (50 mol%) of the compound represented by the following formula (L-1), 39.14 g (37 mol%) of the compound represented by the following formula (L-2), and the following formula (L-3) 10.70 g (13 mol%) of the compound represented by formula (1) is dissolved in 200 g of 2-butanone, and 5.58 g of dimethyl 2,2′-azobis (2-methylpropionate) is further added to the monomer solution. Was prepared. A 1000 mL three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes, then heated to 80 ° C. with stirring, and the prepared monomer solution was added dropwise over 3 hours using a dropping funnel. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization reaction, the polymer solution was cooled to 30 ° C. or less by water cooling, and then poured into 2000 g of methanol, and the precipitated white powder was filtered off. The filtered white powder was washed twice with 400 g of methanol on the slurry, filtered, and dried at 50 ° C. for 17 hours to obtain a white powdered resin (A-1) (78 g, yield 78%). ). Mw of the obtained resin (A-1) was 5,200, Mw / Mn was 1.62, and the residual ratio of the low molecular weight component was 0.03%. Moreover, it has a repeating unit represented by a following formula (A-1) as a result of < ¹³ > C-NMR analysis, The content rate (mol%) of each repeating unit is a / b / c = 50.0 / It was 37.0 / 13.0.

(Synthesis Example 2: Resin (A-2))
In place of the compound represented by the formula (L-3), 19.86 g (25 mol%) of a compound represented by the following formula (L-4) was used, and represented by the formula (L-1). Except that 52.47 g (50 mol%) of the compound to be used and 27.66 g (25 mol%) of the compound represented by the formula (L-2) were used, Similarly, resin (A-2) was obtained (78 g, yield 78%). Mw of the obtained resin (A-2) was 5,490, Mw / Mn was 1.52, and the residual ratio of the low molecular weight component was 0.03%. Moreover, it has a repeating unit represented by a following formula (A-2) as a result of < ¹³ > C-NMR analysis, The content rate (mol%) of each repeating unit is a / b / c = 50.3 / It was 24.7 / 25.0.

(Synthesis Example 3: Resin (A-3))
38.74 g (40 mol%) of the compound represented by the formula (L-1) and 61.26 g (60 mol%) of the compound represented by the formula (L-2) were dissolved in 200 g of 2-butanone. Further, 3.58 g of dimethyl 2,2′-azobis (2-methylpropionate) was added to prepare a monomer solution. A 1000 mL three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes, then heated to 80 ° C. with stirring, and the prepared monomer solution was added dropwise over 3 hours using a dropping funnel. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization reaction, the polymer solution was cooled to 30 ° C. or less by water cooling, and then poured into 2000 g of methanol, and the precipitated white powder was filtered off. The filtered white powder was washed twice with 400 g of methanol on the slurry, filtered, and dried at 50 ° C. for 17 hours to obtain a white powdered resin (A-3) (78 g, 78% yield). ). Mw of the obtained resin (A-3) was 5,400, Mw / Mn was 1.60, and the residual ratio of the low molecular weight component was 0.03%. ^Further, 13 C-NMR analysis revealed that a repeating unit represented by the following formula (A-3), the content of each repeating unit (mol%) is, a / b = 41.0 / 59 . 0.

(Synthesis Example 4: Resin (A-4))
53.93 g (50 mol%) of the compound represented by the formula (L-1), 10.69 g (10 mol%) of the compound represented by the following formula (L-5), and the following formula (L-6) 35.38 g (40 mol%) of the compound represented by formula (1) is dissolved in 200 g of 2-butanone, and 3.58 g of dimethyl 2,2′-azobis (2-methylpropionate) is further added to the monomer solution. Was prepared. A 1000 mL three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes, then heated to 80 ° C. with stirring, and the prepared monomer solution was added dropwise over 3 hours using a dropping funnel. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization reaction, the polymer solution was cooled to 30 ° C. or less by water cooling, and then poured into 2000 g of methanol, and the precipitated white powder was filtered off. The filtered white powder was washed twice with 400 g of methanol on the slurry, filtered, and dried at 50 ° C. for 17 hours to obtain a white powdered resin (A-4) (82 g, yield 82%). ). Mw of the obtained resin (A-4) was 5,800, Mw / Mn was 1.61, and the residual ratio of the low molecular weight component was 0.03%. Moreover, it has a repeating unit represented by a following formula (A-4) as a result of < ¹³ > C-NMR analysis, and the content rate (mol%) of each repeating unit is 53.0 / 9.8 / 37. 2.

(Synthesis Example 5: Resin (A-5))
In place of the compound represented by the formula (L-2), 24.42 g (15 mol%) of a compound represented by the following formula (L-7) was used, and represented by the formula (L-3). In place of the compound, 30.40 g (40 mol%) of the compound represented by the following formula (L-8) was used, and 45.18 g of the compound represented by the formula (L-1) ( (45 mol%) A resin (A-5) was obtained in the same manner as in Synthesis Example 1 except that it was used (75 g, yield 75%). Mw of the obtained resin (A-5) was 6,100, Mw / Mn was 1.73, and the residual ratio of the low molecular weight component was 0.04%. Moreover, as a result of ¹³ C-NMR analysis, it has a repeating unit represented by the following formula (A-5), and the content (mol%) of each repeating unit is a / b / c = 44.1 / It was 15.5 / 40.4.

(Examples 1 to 4 and Reference Example 1: Preparation of resist agent)
Using the resin synthesized in Synthesis Examples 1 to 5, the acid generator, the acid diffusion control agent, and the solvent, the first resist agents (1) to (4) and the second resist agent ( 5) was prepared.

  In addition, the types of the acid generator, the acid diffusion controller, and the solvent that are abbreviated in Table 1 are shown below.

<Acid generator (D)>
(D-1): 1- (4-n-butoxynaphthyl) tetrahydrothiophenium perfluoro-n-butanesulfonate (D-2): triphenylsulfonium / nonafluoro-n-butanesulfonate

<Acid diffusion control agent (E)>
(E-1): tert-butyl-4-hydroxy-1-piperidinecarboxylate (E-2): triphenylsulfonium salicylate

<Solvent (F)>
(F-1): Propylene glycol monomethyl ether acetate (F-2): γ-butyrolactone

(Synthesis Example 6: hydroxyl group-containing resin (B-1))
62.13 g of p-hydroxymethacrylanilide (m-1), 37.87 g of pt-butoxystyrene (m-2), and 10.21 g of azobisisobutyronitrile (AIBN) are dissolved in 300 g of isopropanol (IPA). Then, the polymerization reaction was performed for 6 hours under reflux conditions (82 ° C.). After cooling the reaction vessel with running water, 200 g of ethyl acetate, 140 g of IPA, and 140 g of methanol were added to homogenize, and 600 g of water was further added and left to stand for 1 hour. The viscous polymer that settled in the lower layer was collected and dried under vacuum at 50 ° C. to obtain a hydroxyl group-containing resin (B-1) (yield 70%). Mw of the obtained hydroxyl group-containing resin (B-1) was 8500, and Mw / Mn was 2.08. Moreover, as a result of ¹³ C-NMR analysis, the ratio (molar ratio) of repeating units contained in the obtained hydroxyl group-containing resin (B-1) was (m−1) / (m−2) = 55.4 /. 44.6. The structures of p-hydroxymethacrylanilide (m-1) and pt-butoxystyrene (m-2) are shown below.

(Synthesis Example 7: hydroxyl group-containing resin (B-2))
17.62 g of p-hydroxymethacrylanilide (m-1), 10.22 g of pt-butoxystyrene (m-2), 2-(((trifluoromethyl) sulfonyl) amino) ethyl-1-methacrylate (m- 3) 2.16 g and 2.18 g of AIBN were dissolved in 90 g of IPA, and a polymerization reaction was performed for 6 hours under reflux conditions (82 ° C.). After cooling the reaction vessel with running water, 60 g of ethyl acetate, 42 g of IPA, and 42 g of methanol were added and homogenized, and 180 g of water was further added and left to stand for 1 hour. The viscous polymer that settled in the lower layer was collected and dried under vacuum at 50 ° C. to obtain a hydroxyl group-containing resin (B-2) (yield 77%). Mw of the obtained hydroxyl group-containing resin (B-2) was 7800, and Mw / Mn was 1.50. As a result of ¹³ C-NMR analysis, the ratio (molar ratio) of repeating units contained in the obtained hydroxyl group-containing resin (B-2) was (m−1) / (m−2) / (m−3). ) = 54.2 / 41.3 / 4.5. The structure of 2-(((trifluoromethyl) sulfonyl) amino) ethyl-1-methacrylate (m-3) is shown below.

(Synthesis Example 8: hydroxyl group-containing resin (B-3))
30.66 g of p-hydroxymethacrylanilide (m-1), 15.25 g of pt-butoxystyrene (m-2), 4.10 g of glycidyl methacrylate (m-4), and 3.70 g of AIBN are dissolved in 150 g of IPA. Then, the polymerization reaction was performed for 6 hours under reflux conditions (82 ° C.). After cooling the reaction vessel with running water, 100 g of ethyl acetate, 70 g of IPA and 70 g of methanol were added to the polymerization solution to make a uniform solution, and 300 g of water was further added and left for 1 hour. The viscous polymer that settled in the lower layer was recovered and vacuum dried at 50 ° C. to obtain a hydroxyl group-containing polymer (B-3) (yield 68%). Mw of the obtained hydroxyl group-containing resin (B-3) was 8,200, and Mw / Mn was 1.50. As a result of ¹³ C-NMR analysis, the content (mol%) of each repeating unit was (m−1) / (m−2) / (m−4) = 55.2 / 35.5 / 9. .3. The structure of glycidyl methacrylate (m-4) is shown below.

(Preparation of insolubilized resin composition (A))
Hydroxyl-containing resin (B-1) 100 parts, crosslinking component (C-1) 5 parts, crosslinking component (C-2) 30 parts, solvent (F-3) 524 parts, and solvent (F-4) 2096 parts. After mixing and stirring for 3 hours, an insolubilized resin composition (A) was prepared by filtering using a filter having a pore size of 0.03 μm.

(Preparation of insolubilized resin compositions (B) and (C))
Insolubilized resin compositions (B) and (C) were prepared in the same manner as in the above-mentioned “insolubilized resin composition (A)” except that the formulation shown in Table 2 was used.

  The types of crosslinking components and solvents abbreviated in Table 2 are shown below.

<Crosslinking component (C)>
(C-1): Product name “Nicalak MX-750” (manufactured by Nippon Carbide)
(C-2): Product name “OXIPA” (manufactured by Ube Industries)
(C-3): Pentaerythritol triacrylate

<Solvent (F)>
(F-3): 1-butanol (F-4): 4-methyl-2-pentanol

(Reference Example 2)
A 12-inch silicon wafer was spin-coated with a lower antireflection film (trade name “ARC29A”, manufactured by Brewer Science) using a trade name “CLEAN TRACK ACT12” (manufactured by Tokyo Electron), and then PB (205 (C, 60 seconds) to form a 77 nm-thickness coating film. Using the trade name “CLEAN TRACK ACT12”, spin coat the first resist agent (1), PB (115 ° C., 60 seconds), and then cool (23 ° C., 30 seconds) to coat 150 nm thick. A film was formed. Next, using an ArF immersion exposure apparatus (trade name “XT1250i”, manufactured by ASML), NA: 0.85, Outer / Inner = 0.89 / 0.59 Annular optical conditions, 50 nm line / 200 nm pitch The exposure was carried out through a mask having a mask size of. After PEB (115 ° C., 60 seconds) on a hot plate of the trade name “CLEAN TRACK ACT12”, it was cooled (23 ° C., 30 seconds), and 2.38% tetramethylammonium hydroxide was used with the LD nozzle of the developing cup. Paddle development (30 seconds) was performed using the aqueous solution as a developer, and rinsed with ultrapure water. The substrate A for evaluation on which the first resist pattern was formed was obtained by spin-drying by shaking off at 2000 rpm for 15 seconds.

  On the first resist pattern of the obtained substrate for evaluation A, the insolubilized resin composition (A) was spin-coated using the trade name “CLEAN TRACK ACT12” and applied to a film thickness of 150 nm. PB before washing (130 ° C., 60 seconds) was performed. Using the product name “CLEAN TRACK ACT12”, cooling with a cooling plate at 23 ° C. for 30 seconds, and then using a LD nozzle of the developing cup with a 2.38% tetramethylammonium hydroxide aqueous solution as a developer for paddle development (60 seconds) And rinsed with ultrapure water. Spin-drying was performed by shaking off at 2000 rpm for 15 seconds. After cleaning, PB (165 ° C., 90 seconds) was performed to obtain an evaluation substrate B on which an insolubilized resist pattern was formed.

(Reference Examples 3 to 13)
Each evaluation substrate on which an insolubilized resist pattern was formed in the same manner as in Reference Example 2 except that the first resist agent and the insolubilized resin composition shown in Table 3 were used and the conditions shown in Table 3 were used. B was obtained.

(Example 5)
After spin-coating the second resist agent (5) on the insolubilized resist pattern of the evaluation substrate B obtained in Reference Example 2 using the trade name “CLEAN TRACK ACT12” and PB (100 ° C., 60 seconds) Then, it was cooled (23 ° C., 30 seconds) to form a coating film having a thickness of 150 nm. Using an ArF immersion exposure apparatus, the space of the insolubilized resist pattern through a mask having a mask size of 50 nm line / 200 nm pitch under the optical conditions of NA: 0.85 and Outer / Inner = 0.89 / 0.59 Annular The part was exposed. After PEB (95 ° C., 60 seconds) on a hot plate of the trade name “CLEAN TRACK ACT12”, it was cooled (23 ° C., 30 seconds), and 2.38% tetramethylammonium hydroxide was used in the LD nozzle of the developing cup. Paddle development (30 seconds) was performed using the aqueous solution as a developer, and rinsed with ultrapure water. The substrate for evaluation C on which the second resist pattern was formed was obtained by spin-drying by shaking off at 2000 rpm for 15 seconds. The evaluation result of the pattern of the obtained evaluation substrate C was “◯”.

(Examples 6 to 16)
A second resist pattern was formed in the same manner as in Example 5 except that each evaluation substrate B shown in Table 4 and the second resist agent were used and the conditions shown in Table 4 were used. An evaluation substrate C was obtained. Table 4 shows the evaluation results of the pattern of the obtained evaluation substrate C.

  As is apparent from the results shown in Table 4, when the first resist agent of Examples 1 to 4 is used, the first resist pattern is made into an insolubilized resist pattern that is sufficiently insoluble in the developer and the second resist agent. Is possible.

  According to the resist pattern forming method of the present invention, the pattern gap of the resist pattern can be effectively miniaturized and a pattern exceeding the wavelength limit can be formed favorably and economically. For this reason, the resist pattern forming method of the present invention can be very suitably employed in the field of microfabrication represented by the manufacture of integrated circuit elements that are expected to become increasingly finer in the future.

It is sectional drawing which shows an example of a 1st pattern typically. It is sectional drawing which shows an example of an insolubilized resist pattern typically. It is a top view which shows an example of an insolubilized resist pattern typically. It is sectional drawing which shows typically an example of the state which formed the 2nd resist layer on the insolubilization resist pattern. It is a top view which shows typically an example of the state which formed the line part of the 2nd resist pattern in the space part of the insolubilized resist pattern. It is a top view which shows typically the other example of the state which formed the line part of the 2nd resist pattern in the space part of the insolubilized resist pattern. It is a top view which shows typically an example of the state which formed the line part of the 2nd resist pattern on the line part of the insolubilized resist pattern. It is a side view which shows typically an example of the state which formed the line part of the 2nd resist pattern on the line part of the insolubilized resist pattern.

Explanation of symbols

1: first resist pattern, 1a: first line portion, 1b: first space portion, 2, 22, 32: second resist pattern, 2a, 22a, 32a: second line portion, 2b, 22b, 32b : Second space part, 3: insolubilized resist pattern, 5: insoluble film, 10: substrate, 12: second resist layer, 15: contact hole

Claims (5)

(1) The first resist layer formed on the substrate using the first positive radiation-sensitive resin composition is selectively exposed through a mask and then developed to form a first resist pattern. And a process of
(2) A resist pattern insolubilizing resin composition containing a hydroxyl group-containing resin and an alcohol solvent is applied onto the first resist pattern, and after baking or UV curing, the substrate is washed to form the first resist pattern. A step of making an insolubilized resist pattern insoluble in the developer and the second positive radiation-sensitive resin composition;
(3) forming a second resist layer on the insolubilized resist pattern using a second positive radiation-sensitive resin composition, and selectively exposing the second resist layer through a mask; ,
(4) developing to form a second resist pattern,
The first positive radiation sensitive resin composition used in the step (1) has an acid dissociable group containing 5 to 65 mol% of one or more repeating units represented by the following general formula (1). the positive type radiation-sensitive resin composition containing the resin (provided that the resin having an acid-dissociable group, a polymer compound containing a repeating unit derived from a monomer represented by the following general formula (i), the following A resist pattern forming method which is a polymer compound represented by formula (ii) and polymer compounds represented by formulas (iii-1) to (iii-5) below .

(In the general formula (1), R ¹ represents hydrogen or a methyl group, and a plurality of R ² are (i) each independently, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms. Or a derivative thereof, or a linear or branched alkyl group having 1 to 4 carbon atoms (provided that at least one of R ² is a monovalent polycyclic hydrocarbon group having 7 to 20 carbon atoms) Or (ii) a divalent polycyclic hydrocarbon group having 7 to 20 carbon atoms, each of which is formed by bonding any two of R ^{2 s} to each other, and containing each bonded carbon atom; The remaining R ² represents a linear or branched alkyl group having 1 to 4 carbon atoms, or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof.

(In the general formula (i), R ³⁰ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ³¹ represents an ether bond, ester bond, carbonyl group, hydroxyl group, Or a divalent organic group that may contain an unsaturated bond, R ³² and R ³³ are each independently a hydrogen atom, or an ether bond, an ester bond, a carbonyl group, a hydroxyl group, or an unsaturated bond having 1 to 10 carbon atoms. the containing ^{.R 31} and ^{R 32} or ^{R 31} and ^{R 33} also represents an univalent organic group is binding to which they are attached to one another ^(i.e., in the case of ^{R 31} and ^{R 33} directly ^bonded, the ^{R 32} In this case, a trivalent organic group having 2 to 20 carbon atoms may be formed by combining R ³¹ and R ³² or R ³¹ and R ^33. representing ^{.R 32} and ³³ coupled to which they are attached to one another (i.e., in the case of R ³² is attached via an oxygen atom, directly attached in the case of R ³³⁾ may form a ring together with the carbon atoms, in this case, R ³² and R ³³ together represent a divalent organic group having 2 to 20 carbon atoms, X ′ being a hydroxyl group, a halogen atom, or an ether bond, ester bond, carbonyl group, hydroxyl group, or unsaturated group having 1 to 10 carbon atoms. Represents a monovalent organic group which may contain a bond, and n ′ represents an integer of 0 to 7.))

-C (R in the general formula (1) ² ) ₃ The resist pattern forming method according to claim 1, wherein the group represented by the formula is a group represented by the following general formula (1a), (1b), (1d), or (1e).

(In the general formulas (1a), (1b), (1d), and (1e), R ³ Are each independently a linear or branched alkyl group having 1 to 4 carbon atoms. ) The resist pattern formation method according to claim 1 or 2, wherein the alcohol solvent contained in the resist pattern insolubilized resin composition is a monohydric alcohol having 1 to 8 carbon atoms. The resin containing a hydroxyl group contained in the resist pattern insolubilized resin composition is a resin obtained by polymerizing a monomer component represented by the following general formula (7). The resist pattern formation method as described in 2.

(In the general formula (7), R ¹³ Each independently represents a hydrogen atom or a methyl group, R ¹⁴ Represents a single bond or a linear, branched or cyclic divalent hydrocarbon group. ) The resin containing a hydroxyl group contained in the resist pattern insolubilized resin composition is a monomer represented by the following general formula (8-1) and a monomer represented by the following general formula (8-2). The method for forming a resist pattern according to claim 4, which is a resin obtained by polymerizing at least one of them.

(In the general formula (8-1), R ¹⁵ Represents a hydrogen atom, a methyl group, or a trifluoromethyl group, A represents a methylene group, an ethylene group, or a propylene group, R ¹⁶ Represents a group represented by the following formula (9-1) or a group represented by the following formula (9-2). In the general formula (8-2), R ¹⁵ Represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and R ¹⁷ Represents a methylene group or an alkylene group having 2 to 6 carbon atoms, R ¹⁸ Represents a hydrogen atom, a methyl group, or an ethyl group, and n represents 0 or 1. )

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