JP2018124298A - Pattern forming method and method for manufacturing electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pattern forming method including a double development process, by which only a side wall portion of a negative pattern formed by first development with an organic solvent can be selectively changed into insoluble and can be resolved as a pattern without using an additional process such as etching, a bridge defect between fine resist patterns can be suppressed, and a pattern with high limit resolution can be formed, and to provide a method for manufacturing an electronic device including the above pattern forming method.SOLUTION: The pattern forming method includes, in the following order; (i) a step of forming an active ray-sensitive or radiation-sensitive film by using an active ray-sensitive or radiation-sensitive resin composition comprising a resin (A) including an acid-decomposable group and a crosslinking reactive group; (ii) a step of irradiating the above film with active rays or radiation; (iii) a step of developing the film by using a first developer comprising an organic solvent to remove a region with a low exposure dose to form a negative pattern; (iv) a step of reducing the solubility of a region with a medium exposure dose of the negative pattern with respect to a second developer; and (v) a step of developing the negative pattern by using the second developer to remove a region with a high exposure dose so as to allow only the region with the medium exposure dose to remain as a pattern.SELECTED DRAWING: None

Description

  The present invention relates to a pattern forming method and an electronic device manufacturing method used in a semiconductor manufacturing process such as an IC (Integrated Circuit), a circuit board such as a liquid crystal and a thermal head, and other photofabrication lithography processes. It is about.

  Since the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method for a resist in order to compensate for sensitivity reduction due to light absorption. An example of a positive-type chemical amplification image forming method will be described. The acid generator in the exposed area is decomposed by exposure to generate an acid, and the generated acid is reacted with the reaction catalyst in a post-exposure bake (PEB). Is used to change an alkali-insoluble group to an alkali-soluble group, and an exposed portion is removed by alkali development.

  To reduce the size of semiconductor elements, the exposure light source has become shorter and the projection lens has a higher numerical aperture (high NA). Currently, an exposure machine using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed. ing. When an ArF excimer laser is used as an exposure light source, a compound having an aromatic group essentially exhibits a large absorption in the 193 nm region. Therefore, an ArF excimer laser resist containing a resin having an alicyclic hydrocarbon structure has been developed. (For example, see Patent Documents 1 to 4). Further, as a technique for further increasing the resolving power, a method of filling a high refractive index liquid (hereinafter also referred to as “immersion liquid”) between the projection lens and the sample (ie, immersion method) has been proposed. Further, EUV (Extreme ultra violet) lithography in which exposure is performed with ultraviolet light having a shorter wavelength (13.5 nm) has been proposed.

  In recent years, a negative image forming method including an organic solvent development process in which development is performed using a developer containing an organic solvent (hereinafter also referred to as “organic solvent developer”) is being developed. For example, Patent Document 5 discloses a double development process in which an alkali development process in which development is performed using an alkaline developer and an organic solvent development process is performed as a double patterning technique for further increasing the resolution.

  The double development process will be described with reference to FIG. 1. By exposure, the polarity of the resin in the resist composition becomes high in an area 13 where the light intensity is high (hereinafter referred to as “high exposure area”). In the low intensity area (hereinafter referred to as “low exposure area”) 11, the low exposure area 11 of the actinic ray-sensitive or radiation-sensitive film is converted into an organic solvent developer by utilizing the fact that the low polarity is maintained. (See FIGS. 1A and 1B), and the high exposure region 13 is dissolved in an alkaline developer, so that the intermediate exposure region 12 remains without being dissolved and removed by development. This is a technique in which a line and space pattern having a half pitch is formed (see FIGS. 1B and 1C).

  In Patent Document 6, in order to form a fine pattern, a layer containing a crosslinking reactive material is formed on the first resist pattern, and an acid generated in the first resist pattern by exposure or heat is generated. By diffusing into the layer, a portion adjacent to the side wall of the first resist pattern is cross-linked to obtain a cross-linking spacer, the non-cross-linked portion of the layer and the first resist pattern are removed by etching, A fine pattern forming method is described in which the cross-linking spacer adjacent to the side wall of one resist pattern is obtained as a second pattern.

  In this pattern formation method, a process of etching and removing the cross-linking spacer formed on the upper portion of the first resist pattern is necessary before the etching step. This is because the polar group after decomposition of the acid-decomposable group present in the resist pattern reacts with the cross-linking agent contained in the layer, and this becomes a reaction point, and the upper part of the resist pattern also undergoes an excessive cross-linking reaction. The cause is presumed to be advancing.

JP 2009-114453 A JP 2006-145775 A JP 2001-209181 A JP 2006-16379 A JP 2008-292975 A International Publication No. 2009/009095

  Integrated circuits are becoming more and more integrated, and there is a need for a method for resolving fine patterns more easily. When an additional process such as etching is used as in the technique for obtaining the cross-linked spacer as the second pattern as disclosed in Patent Document 6, the production amount of the device is reduced. In addition, when miniaturization of a resist pattern is required as in recent years, excessive cross-linking causes a bridge defect in a pattern finally obtained, resulting in a decrease in limit resolution.

  However, it is the actual situation that the conventional actinic ray-sensitive or radiation-sensitive resin composition including the above-mentioned prior art does not necessarily satisfy these requirements.

  The present invention has been developed in view of the above circumstances, and in a pattern formation method including a double development process, only the side wall portion of the negative pattern formed by the first organic solvent development uses an additional process such as etching. It is an object of the present invention to provide a pattern forming method that can be resolved as a putter, can further suppress bridge defects between fine resist patterns, and can form a pattern with high limit resolution. . Moreover, this invention makes it a subject to provide the manufacturing method of an electronic device containing this pattern formation method.

In one aspect, the present invention is as follows.
[1]
(I) forming an actinic ray-sensitive or radiation-sensitive film using an actinic ray-sensitive or radiation-sensitive resin composition containing the resin (A) containing an acid-decomposable group and a crosslinkable reactive group;
(Ii) irradiating the film with actinic rays or radiation;
(Iii) developing the film with a first developer containing an organic solvent, removing a low exposure area to form a negative pattern,
(Iv) reducing the solubility of the negative pattern in the intermediate exposure area in the second developer; and (v) developing the negative pattern using the second developer to obtain a high exposure area. The pattern formation method which includes the process of leaving only an intermediate | middle exposure amount area | region as a pattern by removing this in this order.

[2]
The pattern forming method according to [1], wherein the second developer is an alkali developer.

[3]
The pattern forming method according to [1], wherein the second developer contains an organic solvent.

[4]
The pattern forming method according to any one of [1] to [3], wherein the step (iv) includes bringing a treating agent that reacts with the crosslinkable reactive group into contact with the negative pattern.

[5]
The pattern formation method according to any one of [1] to [4], wherein the resin (A) includes a repeating unit having an acid-decomposable group and a crosslinkable reactive group.

[6]
The pattern forming method according to [5], wherein in the repeating unit, the crosslinkable reactive group is included in a site that is eliminated by the action of an acid that is a partial structure of the acid decomposable group.

[7]
The pattern forming method according to [6], wherein the acid-decomposable group is represented by the following general formula (1).

In general formula (1),
R ₁ and R ₂ each independently represent a substituent, L ₁ represents a (n + 1) -valent linking group, X represents a crosslinkable reactive group, n represents an integer of 1 or more, and * represents Represents the bonding position with the main chain of the resin (A). _Two selected from R ₁ , R ₂ and L ₁ may be linked to each other to form a ring.

[8]
The pattern forming method according to [6], wherein the acid-decomposable group is represented by the following general formula (2).

In general formula (2),
R ₁ and R ₂ each independently represent a substituent, R ₃ and R ₄ each independently represent a hydrogen atom or a substituent, L ₂ represents an (n + 1) -valent linking group, and L ₃ Represents a single bond or a divalent linking group, X represents a crosslinkable reactive group, n represents an integer of 1 or more, and * represents a bonding position with the main chain of the resin (A). _Two selected from R ₁ , R ₂ and L ₂ may be connected to each other to form a ring, and R ₃ and R ₄ may be connected to each other to form a ring.

[9]
The manufacturing method of an electronic device containing the pattern formation method of any one of [1]-[8].

  According to the present invention, only the side wall portion of the negative pattern formed by the first organic solvent development can be resolved as a pattern without using an additional process such as etching, and further, a bridge defect between fine resist patterns. It is possible to provide a pattern forming method capable of suppressing the above and forming a pattern with high limit resolution. In addition, according to the present invention, it is possible to provide an electronic device manufacturing method including this pattern forming method.

The figure for demonstrating a double image development process roughly.

Hereinafter, embodiments of the present invention will be described in detail.
In the description of the group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

  In the present specification, “active light” or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), etc. To do. In the present invention, light means actinic rays or radiation.

  In addition, “exposure” in the present specification is not limited to exposure to far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light and the like represented by mercury lamps and excimer lasers, but also electron beams, ion beams, and the like, unless otherwise specified. The exposure with the particle beam is also included in the exposure.

  In the specification of the present application, “to” is used in the sense of including the numerical values described before and after it as lower and upper limits.

In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.
Hereinafter, the pattern forming method of the present invention will be described in detail, and then the actinic ray-sensitive or radiation-sensitive resin composition used in the pattern-forming method of the present invention (hereinafter referred to as “the actinic ray-sensitive or sensitive of the present invention”). The radiation resin composition "or" the composition of the present invention "is also described in detail.

<Pattern formation method>
The pattern forming method of the present invention comprises:
A step of forming an actinic ray-sensitive or radiation-sensitive film using the actinic ray-sensitive or radiation-sensitive resin composition containing the resin (A) containing an acid-decomposable group and a crosslinkable reactive group (hereinafter referred to as “film”) Forming process)),
A step of irradiating the film with actinic rays or radiation (hereinafter referred to as “exposure step”),
A step of developing the film with a first developer containing an organic solvent to remove a low exposure area and forming a negative pattern (hereinafter referred to as a “first development step”);
A step of lowering the solubility of the negative pattern in the intermediate exposure amount region in the second developer (hereinafter referred to as “insolubilization step”), and developing the negative pattern using the second developer, A step of removing only the intermediate exposure amount region as a pattern by removing the high exposure amount region (hereinafter referred to as “second development step”).
In this order.

  In the present invention, the “low exposure region” is a region where the exposure amount is insufficient and the decomposition of the acid-decomposable group in the resin contained in the actinic ray-sensitive or radiation-sensitive resin composition has not progressed. "High exposure area" means an area where the exposure is sufficient and the acid-decomposable group has completely decomposed, and "intermediate exposure area" means the decomposition of the acid-decomposable group. Means an area where a part is progressing.

The pattern forming method of the present invention comprises an actinic ray-sensitive or radiation-sensitive composition containing a resin containing an acid-decomposable group and a crosslinkable reactive group (hereinafter also referred to as “resin (A)”) as a pattern-forming composition. One of the features is that an insolubilization step is included between the use of the conductive resin composition and the first development step and the second development step.
In the first development step, the low exposure area of the actinic ray-sensitive or radiation-sensitive film is removed by the first developer (organic solvent developer) to form a negative pattern,
In the subsequent insolubilization step, only the intermediate exposure area in the negative pattern (actinic ray-sensitive or radiation-sensitive film) is selectively crosslinked to reduce the solubility of the intermediate exposure area in the second developer (insolubilization). To do).

  This insolubilization process eliminates the difference in the degree of insolubilization between the high exposure area and the intermediate exposure area of the negative pattern, dissolves the high exposure area, which originally had a high dissolution rate, and the intermediate exposure area remains. Thus, only the side wall portion can be insolubilized, and the occurrence of the second development bridge defect can be suppressed.

  In the pattern formation method of this invention, the 1st developing solution used at a 1st image development process is a developing solution (organic solvent developing solution) containing an organic solvent.

  On the other hand, as a developer that can be used in the second development step, both a developer containing an alkaline aqueous solution (alkali developer) and an organic solvent developer can be used.

  Hereinafter, each step will be described in detail, and then the actinic ray-sensitive or radiation-sensitive resin composition containing the resin (A) will be described in detail.

[Film formation process]
The film forming step is a step of forming a film (hereinafter also referred to as “active light sensitive or radiation sensitive film”) on the substrate using the actinic ray sensitive or radiation sensitive resin composition.

  The method for forming the actinic ray-sensitive or radiation-sensitive film on the substrate using the actinic ray-sensitive or radiation-sensitive resin composition is not particularly limited, and a known method can be adopted. Especially, the method of apply | coating the said actinic-light sensitive or radiation sensitive resin composition on a board | substrate from the point which adjustment of the thickness of a film | membrane is easier is mentioned.

  The application method is not particularly limited, and a known method can be adopted. Among these, spin coating is preferably used in the semiconductor manufacturing field.

  Moreover, you may implement the drying process for removing a solvent as needed after apply | coating actinic-ray-sensitive or radiation-sensitive resin composition. The method for the drying treatment is not particularly limited, and examples thereof include heat treatment and air drying treatment.

<Actinic ray-sensitive or radiation-sensitive film>
The receding contact angle of a film (actinic ray-sensitive or radiation-sensitive film) formed using the actinic ray-sensitive or radiation-sensitive resin composition in the present invention is 70 at a temperature of 23 ± 3 ° C. and a humidity of 45 ± 5%. It is preferably at least 0 °, more preferably at least 75 °, and even more preferably 75 to 85 °. When the receding contact angle of the actinic ray-sensitive or radiation-sensitive film is in the above range, it is suitable for exposure through an immersion medium.

  If the receding contact angle is too small, it cannot be suitably used for exposure through an immersion medium, and the effect of reducing water residue (watermark) defects cannot be sufficiently exhibited. In order to realize a preferable receding contact angle, it is preferable to include the hydrophobic resin in the actinic ray-sensitive or radiation-sensitive composition. Alternatively, the receding contact angle may be improved by forming a coating layer (so-called “topcoat”) of a hydrophobic resin composition on the actinic ray-sensitive or radiation-sensitive film.

  The topcoat composition is a hydrophobic resin described later and at least one selected from the group consisting of the following (A1), (A2) and (A3) (hereinafter referred to as “additive (A)” or “compound (A ) ”)).

(A1) Basic compound or base generator (A2) A compound containing at least one bond or group selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond and an ester bond (A3 ) Onium salt.

  The content of (A1) to (A3) is preferably 1 to 25% by mass, more preferably 2.5 to 20% by mass, based on the total solid content of the topcoat composition.

  The basic compound that can be contained in the topcoat composition is preferably an organic basic compound, and more preferably a nitrogen-containing basic compound.

  A compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond and an ester bond (hereinafter referred to as “compound (A2)” or The “additive (A2)”) will be described below.

  As described above, the compound (A2) is a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond and an ester bond.

  As described above, the compound (A2) includes at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond. In one embodiment of the present invention, the compound (A2) preferably has two or more groups or bonds selected from the above group, more preferably three or more, and still more preferably four or more. In this case, groups or bonds selected from an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond and an ester bond contained in a plurality of compounds (A2) may be the same or different. Good.

  In one embodiment of the present invention, the compound (A2) has a molecular weight of preferably 3000 or less, more preferably 2500 or less, still more preferably 2000 or less, and particularly preferably 1500 or less.

  In one embodiment of the present invention, the number of carbon atoms contained in the compound (A2) is preferably 8 or more, more preferably 9 or more, and still more preferably 10 or more.

  In one embodiment of the present invention, the number of carbon atoms contained in the compound (A2) is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.

  In one embodiment of the present invention, the compound (A2) is preferably a compound having a boiling point of 200 ° C. or higher, more preferably a compound having a boiling point of 220 ° C. or higher, and a compound having a boiling point of 240 ° C. or higher. More preferably it is.

  In one embodiment of the present invention, the compound (A2) is preferably a compound having an ether bond, preferably two or more ether bonds, more preferably three or more, and four or more. More preferably.

  In one embodiment of the present invention, the compound (A2) further preferably contains a repeating unit containing an oxyalkylene structure represented by the following general formula (1).

Where
R ₁₁ represents an alkylene group which may have a substituent,
n represents an integer of 2 or more,
* Represents a bond.

The number of carbon atoms of the alkylene group represented by R ₁₁ in the general formula (1) is not particularly limited, but is preferably 1 to 15, more preferably 1 to 5, and 2 or 3. More preferably, 2 is particularly preferable. When this alkylene group has a substituent, the substituent is not particularly limited, but is preferably an alkyl group (preferably having 1 to 10 carbon atoms), for example.

  n is preferably an integer of 2 to 20, and among them, it is more preferably 10 or less because the DOF becomes larger.

  The average value of n is preferably 20 or less, more preferably 2 to 10, more preferably 2 to 8, and particularly preferably 4 to 6 because the DOF becomes larger. preferable. Here, the “average value of n” means that the weight average molecular weight of the compound (A2) is measured by GPC (Gel Permeation Chromatography), and is determined so that the obtained weight average molecular weight matches the general formula Mean value. If n is not an integer, round it off.

A plurality of R ₁₁ may be the same or different.

  Moreover, it is preferable that the compound which has the partial structure represented by the said General formula (1) is a compound represented by the following general formula (1-1) from the reason for DOF becoming larger.

Where
Definition of R _11, specific examples and preferred embodiments are the same as R ₁₁ in general formula (1).

R ₁₂ and R ₁₃ each independently represents a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1-15. R ₁₂ and R ₁₃ may combine with each other to form a ring.

  m represents an integer of 1 or more. m is preferably an integer of 1 to 20, and among them, it is more preferably 10 or less for the reason that DOF becomes larger.

  The average value of m is preferably 20 or less, more preferably 1 to 10, more preferably 1 to 8, and particularly preferably 4 to 6 because the DOF becomes larger. preferable. Here, the “average value of m” is synonymous with the “average value of n” described above.

When m is 2 or more, a plurality of R ₁₁ may be the same or different.

  In one embodiment of the present invention, the compound having a partial structure represented by the general formula (1) is preferably an alkylene glycol containing at least two ether bonds.

Compound (A2) may be a commercially available product, or may be synthesized by a known method.
Although the specific example of a compound (A2) is given to the following, this invention is not limited to these.

  The topcoat composition can contain an onium salt that is a weak acid relative to the acid generator. When an acid generated from an acid generator upon irradiation with actinic rays or radiation collides with an onium salt having an unreacted weak acid anion, an onium salt having a strong acid anion is generated by releasing a weak acid by salt exchange. In this process, the strong acid is exchanged with a weak acid having a lower catalytic ability, so that the acid is apparently deactivated and the acid diffusion can be controlled.

  The onium salt that is a weak acid relative to the acid generator is preferably a compound represented by the following general formulas (d1-1) to (d1-3).

In the formula, R ⁵¹ represents a hydrocarbon group which may have a substituent, and Z ^2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, a carbon adjacent to S). R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkylene group or an arylene group, and Rf is a fluorine atom. Each of the M ⁺ is independently a sulfonium or iodonium cation.

Preferable examples of the sulfonium cation or iodonium cation represented by M ⁺ include a sulfonium cation exemplified by the general formula (ZI) and an iodonium cation exemplified by the general formula (ZII).

  The thickness of the actinic ray-sensitive or radiation-sensitive film is not particularly limited, but is preferably 1 to 500 nm, more preferably 1 to 100 nm, because a highly accurate fine pattern can be formed. .

[Exposure process]
The exposure step is a step of exposing the film formed in the film formation step. More specifically, it is a step of selectively exposing the film so that a desired pattern is formed. Thereby, the film is exposed in a pattern, and the solubility of the actinic ray-sensitive or radiation-sensitive film changes only in the exposed part.

  “Exposing” intends to irradiate actinic rays or radiation.

  The light used for the exposure is not particularly limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams. Preferably, it is far ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less, and still more preferably 1 to 200 nm.

More specifically, a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F ₂ excimer laser (157 nm), an X-ray, an EUV (13 nm), an electron beam, and the like can be mentioned. ArF excimer laser, EUV or electron beam is preferable, and ArF excimer laser is more preferable.

The method for selectively exposing the film is not particularly limited, and a known method can be used. For example, a binary mask (Binary-Mask) in which the light transmittance of the light shielding portion is 0% or a halftone phase shift mask (HT-Mask) in which the light transmittance of the light shielding portion is 6% can be used.

  In general, a binary mask is used in which a chromium film, a chromium oxide film, or the like is formed on a quartz glass substrate as a light shielding portion.

  As the halftone phase shift mask, generally, a quartz glass substrate on which a MoSi (molybdenum silicide) film, a chromium film, a chromium oxide film, a silicon oxynitride film, or the like is formed as a light shielding portion is used.

  In the present invention, the exposure is not limited to exposure through a photomask, and selective exposure (pattern exposure) may be performed by exposure without using a photomask, for example, drawing with an electron beam or the like.

  This step may include multiple exposures.

(Heat treatment)
Before the exposure step, the film may be subjected to heat treatment (PB: Prebake). Heat treatment (PB) may be performed a plurality of times.
Moreover, you may perform a heat processing (PEB: Post Exposure Bake) with respect to an actinic-light sensitive or radiation sensitive film | membrane after an exposure process. The heat treatment (PEB) may be performed a plurality of times.

  The reaction of the exposed part is promoted by the heat treatment, and the sensitivity and pattern profile are further improved.

  In both PB and PEB, the temperature of the heat treatment is preferably 70 to 130 ° C, more preferably 80 to 120 ° C.

  For both PB and PEB, the heat treatment time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and even more preferably 30 to 90 seconds.

  For both PB and PEB, the heat treatment can be performed by means provided in a normal exposure / development machine, and may be performed using a hot plate or the like.

(Preferred embodiment: immersion exposure)
As a suitable aspect of exposure, for example, liquid immersion exposure can be mentioned. By using immersion exposure, a finer pattern can be formed. Note that immersion exposure can be combined with super-resolution techniques such as a phase shift method and a modified illumination method.

  The immersion liquid used for immersion exposure is transparent to the exposure wavelength and is refracted to minimize distortion of the optical image projected on the actinic ray-sensitive or radiation-sensitive film. Liquids with the lowest possible temperature coefficient are preferred. In particular, when the exposure light source is an ArF excimer laser (wavelength: 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-described viewpoints.

  When water is used as the immersion liquid, an additive (liquid) that decreases the surface tension of water and increases the surface activity may be added in a small proportion. This additive preferably does not dissolve the actinic ray-sensitive or radiation-sensitive film and can ignore the influence on the optical coating on the lower surface of the lens element.

  As such an additive, for example, an aliphatic alcohol having a refractive index substantially equal to that of water is preferable, and specific examples include methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage that the change in the refractive index of the entire liquid can be made extremely small can be obtained.

  On the other hand, when an opaque material or impurities whose refractive index is significantly different from water are mixed with respect to 193 nm light, the optical image projected on the resist is distorted. For this reason, distilled water is preferable as the water to be used. Further, pure water filtered through an ion exchange filter or the like may be used.

  The water used as the immersion liquid preferably has an electric resistance of 18.3 MΩcm or more, a TOC (organic substance concentration) of 20 ppb or less, and is preferably deaerated.

Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive for increasing the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

  In the immersion exposure, the surface of the actinic ray-sensitive or radiation-sensitive film may be washed with an aqueous chemical solution before exposure and / or after exposure (before heat treatment).

[Development process]
The pattern forming method of the present invention includes at least a first development step and a second development step as the development step.

<First development process>
The first development step is a step of developing the film exposed in the exposure step using a first developer containing an organic solvent to form a negative pattern.

  In this step, the low exposure amount region is dissolved by the organic solvent developer that is the first developer, and a so-called negative pattern is formed.

(First developer)
The organic solvent developer which is the first developer contains an organic solvent as a main component. The main component means that the content of the organic solvent is more than 50% by mass with respect to the total amount of the developer.

  The organic solvent contained in the organic developer is not particularly limited, and examples thereof include polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. . Moreover, these mixed solvents may be sufficient.

  Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.

  Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl. Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, isoamyl acetate Butyl butanoate, methyl 2-hydroxyisobutyrate, isobutyl isobutyrate, butyl propionate and the like.

  Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, alcohols such as n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, Diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butano It can be mentioned glycol ether solvents such as Le.

  Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.

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

  Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.

  In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents and ester solvents, and in particular, butyl acetate or ketone as the ester solvent. A developer containing methyl amyl ketone (2-heptanone) as a system solvent is preferred.

  A plurality of organic solvents may be mixed, or may be used by mixing with other solvents or water. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.

  That is, the amount of the organic solvent used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.

  The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the organic developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, and temperature uniformity in the wafer surface is improved. As a result, dimensional uniformity in the wafer surface. Improves.

  An appropriate amount of a surfactant can be added to the organic developer as required.

  The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, US Pat. No. 5,405,720, etc. The surfactants described in US Pat. Nos. 5,360,692, 5,298,881, 5,296,330, 5,346,098, 5,576,143, 5,294,511, and 5,824,451 can be mentioned. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.

  The addition amount of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

(Development method)
As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied.

When the above various development methods include the step of discharging the developer from the developing nozzle of the developing device toward the actinic ray-sensitive or radiation-sensitive film, the discharge pressure of the discharged developer (the discharge developer The flow rate per unit area) is, for example, preferably 2 mL / sec / mm ² or less, more preferably 1.5 mL / sec / mm ² or less, and further preferably 1 mL / sec / mm ² or less. Although there is no particular lower limit of the flow rate, 0.2 mL / sec / mm ² or more is preferable in consideration of throughput. Details thereof are described in paragraphs [0022] to [0029] of JP 2010-232550 A in particular.

In addition, after the step of developing using a developer containing an organic solvent, a step of stopping development may be performed while substituting with another solvent. <Second Development Step>
In the second development step, a high exposure amount region in the negative pattern after insolubilization processing described later is removed. As the second developer used in the second development step, either an organic solvent developer or an alkali developer can be used.

(Second developer)
Organic solvent developer As the organic solvent developer that can be used in the second development step, the description of the organic solvent developer described in the first development step can be used.

  In the second development step, when an organic solvent developer (hereinafter referred to as “second organic solvent developer”) is used as the second developer, the second organic solvent developer is more suitable for the first development. From the viewpoint of improving the LWR, it is more hydrophilic than the organic solvent developer (hereinafter referred to as “first organic solvent developer”). The SP value (solubility parameter) of the second organic solvent developer is preferably larger than the SP value of the first organic solvent developer. The ClogP value (solubility parameter) of the first organic solvent developer is preferably smaller than the ClogP value of the second organic solvent developer. Specific examples include acetone, methyl ethyl ketone, 3-pentanone, cyclohexanone, PGMEA, PGME, ethyl acetate, dimethylformamide and the like.

Alkali developer The type of the alkaline aqueous solution contained in the alkali developer that can be used in the second development step is not particularly limited. For example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, Inorganic alkalis such as aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine, Alkaline aqueous solutions such as alcohol amines such as triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and pihelidine can be used.

  Appropriate amounts of alcohols and surfactants can be added to the alkaline aqueous solution. Specific examples and usage amounts of the surfactant are the same as those of the organic developer described later.

The alkali concentration of the aqueous alkali solution is usually 0.1 to 20% by mass.
The pH of the alkaline aqueous solution is usually 10.0 to 15.0.

(Development method)
As the developing method in the second developing step, the description of the developing method described in the first developing step can be used.

[Insolubilization process]
The pattern forming method of the present invention includes an insolubilization step between the first development step and the second development step. As described above, the insolubilization step is a step of selectively cross-linking only the intermediate exposure amount region in the negative pattern to reduce (solubilize) the solubility of the intermediate exposure amount region in the second developer. .

  The insolubilization treatment is a step of reducing the solubility in a solvent by crosslinking the resist pattern.

  In one embodiment of the present invention, the insolubilization treatment is a processing agent that reacts with a crosslinkable reactive group contained in the resin (A) in the negative pattern (active light sensitive or radiation sensitive film) after the first development. (Hereinafter referred to as “crosslinking agent”).

  Specifically, for example, the film or pattern is immersed in a tank filled with a solution in which a crosslinking agent is dissolved (hereinafter also referred to as “crosslinking treatment liquid” or the like) for a predetermined time. Also, a spin coating method, a spray method similar to development, a paddle method, a dynamic dispensing method, or the like can be used.

  As the crosslinking agent, a low molecular or high molecular compound having a functional group that reacts with the crosslinkable reactive group X in the acid decomposable group of the acid decomposable resin (hereinafter referred to as “reactive functional group”) is used. be able to. Since it is necessary to reduce the solubility of the acid-decomposable resin by reacting with a plurality of crosslinkable groups X in the acid-decomposable resin, it is desirable to have at least two reactive functional groups of the crosslinking agent.

  Preferred examples of the reactive functional group of the crosslinking agent include acid anhydride, isocyanate group, methoxymethyl group, 2-methoxyethoxymethyl group, phosphoric chloride, boric acid, thiol group, thioether group, carbonyl group, aldehyde group, NO Group, amino group, acryloyloxy group, methacryloyloxy group, vinyl group, vinyloxy group, acid chloride, epoxy group, oxetane group, halogenated silyl group, silanol group, metal salts such as zinc oxide and zinc chloride. From the viewpoint of crosslinking efficiency and ease of handling, acid anhydride, isocyanate group, methoxymethyl group, 2-methoxyethoxymethyl group, thiol group, acryloyloxy group, methacryloyloxy group, vinyl group, vinyloxy group, acid chloride, epoxy group Oxetane group, silyl halide group, silanol group and metal salt are more preferable, and acid anhydride, isocyanate group, methoxymethyl group, thiol group, acryloyloxy group, methacryloyloxy group, vinyl group and vinyloxy group are particularly preferable.

  Moreover, the compound mentioned above as a crosslinking agent which the actinic-ray-sensitive or radiation-sensitive resin composition of this invention mentioned later can contain can also be used in this insolubilization process.

  As the solvent, any solvent that dissolves the crosslinking agent and does not dissolve the resist film can be preferably used. Examples thereof include alcohol solvents such as methyl isobutyl carbinol, ketone solvents such as methyl isobutyl ketone, ester solvents such as butyl acetate, ether solvents such as t-butyl methyl ether, or a mixed solvent thereof. . Moreover, the solvent mentioned in description of the organic solvent developing solution, and the solvent mentioned in the rinsing liquid for organic solvent development mentioned later can also be used.

  A catalyst may be added separately for the purpose of increasing the reactivity of the crosslinking agent. Examples of the catalyst for accelerating such a reaction include acids such as p-toluenesulfonic acid (TsOH) and methanesulfonic acid (MsOH), N, N-dimethylaminopyridine (DMAP), 1,4-diazabicyclo [2.2 .2] Amines such as octane (DABCO) and triethylenediamine, tin salts such as dibutyltin dilaurate, carboxylates such as lead naphthenate and potassium acetate, phosphorus compounds such as triethylphosphine, azobisisobutyronitrile And thermal radical initiators such as 2,2′-azobis (methyl isobutyrate), and photoradical initiators such as 2-ethylanthraquinone and 4,4′-dimethoxybenzyl.

(Heat treatment)
Heat treatment may be performed after the insolubilization step. The heat treatment accelerates the cross-linking reaction between the cross-linkable resin and the cross-linking agent and further improves the resolution and the like.

  The temperature of the heat treatment is preferably 50 to 220 ° C, and more preferably 90 to 150 ° C.

  The time for the heat treatment is preferably 10 to 300 seconds, more preferably 20 to 180 seconds, and further preferably 30 to 90 seconds.

  The heat treatment can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.

(Rinse treatment)
After the development step or the insolubilization step, it is preferable to use a rinse solution as necessary.
The rinse liquid is not particularly limited as long as the actinic ray-sensitive or radiation-sensitive film is not dissolved.
As the rinsing liquid in the rinsing step performed after the alkali development step, pure water can be used, and an appropriate amount of a surfactant can be added and used.

  The rinsing liquid used in the rinsing step after organic solvent development or insolubilization treatment is at least one selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. It is preferably a rinsing liquid containing various types of organic solvents, and is a rinsing liquid containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents. More preferably, it is more preferably a rinsing liquid containing an alcohol solvent or an ester solvent, particularly preferably a rinsing liquid containing a monohydric alcohol, containing a monohydric alcohol having 5 or more carbon atoms. Most preferably, it is a rinse solution.

  Specific examples of the hydrocarbon solvent, ketone solvent, ester solvent, alcohol solvent, amide solvent and ether solvent are the same as those of the organic developer described above.

  Examples of the monohydric alcohol include linear, branched, and cyclic monohydric alcohols. More specifically, 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1 -Pentanol, 3-methyl-1-butanol and the like.

  As the rinsing liquid containing a hydrocarbon solvent, a hydrocarbon compound having 6 to 30 carbon atoms is preferable, a hydrocarbon compound having 8 to 30 carbon atoms is more preferable, and a hydrocarbon compound having 8 to 30 carbon atoms is more preferable. A hydrocarbon compound having 10 to 30 carbon atoms is particularly preferred. Especially, pattern collapse is suppressed by using the rinse liquid containing a decane and / or undecane.

  When an ester solvent is used as the rinsing liquid, a glycol ether solvent may be used in addition to the ester solvent (one or more). Specific examples in this case include using an ester solvent (preferably butyl acetate) as a main component and a glycol ether solvent (preferably propylene glycol monomethyl ether (PGME)) as a subcomponent. Thereby, residue defects are suppressed.

  The rinse liquid may contain a plurality of solvents. Moreover, the rinse liquid may contain an organic solvent other than the above.

  The water content of the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, better development characteristics can be obtained.

  The vapor pressure of the rinse liquid is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C., more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

  An appropriate amount of a surfactant can be added to the rinse solution. Specific examples and usage amounts of the surfactant are the same as those of the organic developer described above.

  In the rinsing process, the wafer that has been developed or insolubilized is cleaned using the rinsing liquid. The cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), and the like can be applied. Among these, a method of performing a cleaning process by a spin coating method, rotating the substrate at a rotational speed of 2000 rpm to 4000 rpm after cleaning, and removing the rinse liquid from the substrate is preferable. Moreover, it is preferable to perform a heat treatment (Post Bake) after the rinsing treatment. The developer and the rinsing liquid remaining between the patterns and inside the patterns are removed by heat treatment. The heat treatment after the rinsing treatment is usually performed at 40 to 160 ° C., preferably 70 to 95 ° C., and usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

  In general, the pattern obtained by the pattern forming method of the present invention is suitably used as an etching mask for a semiconductor device, but can also be used for other purposes. As other applications, for example, guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8 Pages 4815-4823), use as a core material (core) of a so-called spacer process (for example, JP-A-3-270227, JP-A-2013-164509, etc.).

  A method for improving the surface roughness of the pattern may be applied to the pattern formed by the method of the present invention. As a method for improving the surface roughness of the pattern, for example, a method of treating a resist pattern with a plasma of a hydrogen-containing gas disclosed in International Publication No. 2014/002808 can be mentioned. In addition, JP-A-2004-235468, US Publication No. 2010/0020297, JP-A-2009-19969, Proc. of SPIE Vol. 8328 83280N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement” may be applied.

  The pattern forming method of the invention can also be used for guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8 Pages 4815-4823).

  Further, the resist pattern formed by the above method can be used as a core material (core) of a spacer process disclosed in, for example, JP-A-3-270227 and JP-A-2013-164509.

<Actinic ray-sensitive or radiation-sensitive resin composition>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a resin (hereinafter, referred to as “acid-decomposable group”) that decomposes by the action of an acid to generate a polar group and a crosslinkable reactive group (hereinafter referred to as “resin”). "Resin (A)" or "acid-decomposable resin").

[Resin (A)]
The resin (A) is an acid-decomposable resin having an acid-decomposable group that is decomposed by the action of an acid to generate a polar group in the main chain or side chain of the resin or in both the main chain and the side chain. Resin (A) increases in polarity by the action of an acid, increases in solubility in an alkaline developer, and decreases in solubility in an organic solvent.

<Acid-decomposable group>
The acid-decomposable group contained in the resin (A) preferably has a structure in which an alkali-soluble group is protected by a group that decomposes and leaves by the action of an acid.

  Preferred examples of the polar group include a carboxy group, a fluorinated alcohol group (preferably hexafluoroisopropanol), and a sulfonic acid group.

  A preferable group as the acid-decomposable group is a group obtained by substituting the hydrogen atom of these alkali-soluble groups with a group capable of leaving with an acid.

Examples of the group leaving with an acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), -C (R ₀₁ ) (R ₀₂ ). ) (OR ₃₉ ) and the like.

In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

R _{01 and} R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

  The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

<Crosslinkable reactive group>
Examples of the crosslinkable reactive group include hydroxyl group, thiol group, amino group, acryloyloxy group, methacryloyloxy group, epoxy group, oxetane group, isocyanate group, aziridine group, oxazoline group, vinyl group, vinyloxy group, cyano group, halogen Silyl group, silanol group, carboxyl group, ester group, and the like. From the viewpoint of crosslinking efficiency and ease of handling, X is preferably a hydroxyl group, a thiol group, an amino group, an acryloyloxy group, a methacryloyloxy group, a vinyl group, or a vinyloxy group, and a hydroxyl group, a thiol group, an acryloyloxy group, or a methacryloyloxy group. More preferred are a vinyl group and an amino group.

  In one embodiment of the present invention, when the crosslinkable reactive group is a hydroxyl group, a thiol group, or an amino group, the smaller the steric hindrance, the higher the crosslinking reactivity. Therefore, the carbon atom to which these groups are linked is primary. > Second order> Third order is preferred.

<Acid-decomposable group having a crosslinkable reactive group as a protecting group>
In one embodiment of the present invention, the resin (A) includes an acid-decomposable group having a crosslinkable reactive group at a site (hereinafter also referred to as “protecting group”) that is eliminated by the action of an acid in the acid-decomposable group. It is preferable to include.

  In an acid-decomposable resin containing an acid-decomposable group having a crosslinkable reactive group as a protective group, the acid-decomposable group is decomposed by the acid generated by exposure in the high exposure range, and the crosslinkable reactive group is detached from the resin. To do. On the other hand, in the intermediate exposure area and the low exposure area, the acid crosslinkable group is not decomposed by the acid, and the crosslinkable reactive group remains linked to the resin.

  When the resin (A) contains an acid-decomposable group having a crosslinkable reactive group in the protective group, in the insolubilization step in the pattern forming method of the present invention, the intermediate exposure region is selectively crosslinked to form the second developer. Can be effectively reduced. For this reason, since the solubility of a high exposure area | region does not fall, a bridge | bridging defect can be improved dramatically.

  The resin (A) preferably has an acid-decomposable group represented by the following general formula (1) or (2).

In general formula (1),
R ₁ and R ₂ each independently represent a substituent, L ₁ represents a (n + 1) -valent linking group, X represents a crosslinkable reactive group, n represents an integer of 1 or more, and * represents Represents the bonding position with the main chain of the resin (A). _Two selected from R ₁ , R ₂ and L ₁ may be linked to each other to form a ring.

In general formula (2),
R ₁ and R ₂ each independently represent a substituent, R ₃ and R ₄ each independently represent a hydrogen atom or a substituent, L ₂ represents an (n + 1) -valent linking group, and L ₃ Represents a single bond or a divalent linking group, X represents a crosslinkable reactive group, n represents an integer of 1 or more, and * represents a bonding position with the main chain of the resin (A). _Two selected from R ₁ , R ₂ and L ₂ may be connected to each other to form a ring, and R ₃ and R ₄ may be connected to each other to form a ring.

The general formula (1) will be described in more detail.
Examples of the substituent represented by R ₁ and R ₂ in the general formula (1) include a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, i Examples thereof include alkyl groups such as -propyl group, sec-butyl group, t-butyl group and t-amyl group, and alicyclic hydrocarbon groups such as cyclopentyl group and cyclohexyl group.
In one embodiment of the present invention, at least one of R ₁ and R ₂ may be an alkyl group having 2 or more carbon atoms, or both may be an alkyl group having 2 or more carbon atoms.

  Examples of the crosslinkable reactive group X include a hydroxyl group, a thiol group, an amino group, an acryloyloxy group, a methacryloyloxy group, an epoxy group, an oxetane group, an isocyanate group, an aziridine group, an oxazoline group, a vinyl group, a vinyloxy group, a cyano group, Examples thereof include a halogenated silyl group, a silanol group, a carboxyl group, and an ester group. From the viewpoint of crosslinking efficiency and ease of handling, X is preferably a hydroxyl group, a thiol group, an amino group, an acryloyloxy group, a methacryloyloxy group, a vinyl group, or a vinyloxy group, and a hydroxyl group, a thiol group, an acryloyloxy group, or a methacryloyloxy group. More preferred are a vinyl group and an amino group.

  In one embodiment of the present invention, when the crosslinkable reactive group X is a hydroxyl group, a thiol group, or an amino group, the smaller the steric hindrance, the higher the crosslinking reactivity. Therefore, the carbon atom to which these groups are linked is Preferred in the order of first grade> second grade> third grade.

N representing the number of substitutions of X with respect to L ₁ is preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.

In one embodiment of the present invention, the linking group L ₁ is preferably a chain structure, a branched structure, a polycyclic structure, or a monocyclic structure.

Preferred examples of the linking group L ₁ include methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl. Group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1 , 12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-diyl group Linear alkanediyl groups such as
Propane-1,2-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-2,2-diyl group, 1-methylbutane-1,3-diyl group, 2-methyl Branched alkanediyl groups such as propane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group Valent alicyclic saturated hydrocarbon group;
A polycyclic hydrocarbon group such as a norbornane ring, a tricyclodecane ring, a tetracyclododecane ring, and an adamantane ring;
Examples include ether groups such as (poly) ethyleneoxy groups and (poly) propyleneoxy groups.

The —CH ₂ — group contained in the linear alkanediyl group, branched alkanediyl group, and divalent alicyclic saturated hydrocarbon group includes —NH—, —O—, and —C (O )-May be replaced with one or more selected.

In the general formula (1), _two selected from R ₁ , R ₂ and L ₁ may be linked to each other to form a ring.

The ring formed by connecting two selected from R ₁ , R ₂ and L ₁ to each other may be either a single ring or a polycycle. For example, cyclobutane, cyclopentane, cyclohexane, cycloheptane and the like can be mentioned.

Next, the general formula (2) will be described in more detail.
The substituent represented by R ₁ and R ₂ in the general formula (2), the crosslinkable reactive group represented by X, and n are represented by R ₁ and R ₂ in the general formula (1). It is synonymous with a substituent, the crosslinkable reactive group represented by X, and n.
Preferable examples of the linking group L ₂ include a linear alkanediyl group, a branched alkanediyl group, a divalent alicyclic saturated hydrocarbon group exemplified in L ₁ in the above general formula (1), a polycyclic ring Specific examples similar to those of the formula hydrocarbon group can be given.

Further, linear alkanediyl group of L _2, branched alkanediyl group, a divalent alicyclic saturated hydrocarbon group, and a divalent polycyclic hydrocarbon group, similar to the L _1, -CH _2- may be replaced with one or more selected from -NH-, -O- and -C (O)-.

In general formula (2), _two selected from R ₁ , R ₂ and L ₂ may be linked to each other to form a ring. The ring formed is preferably a single ring, and examples thereof include cyclobutane, cyclopentane, cyclohexane, cycloheptane and the like.

Examples of the substituent represented by R ₃ and R ₄ include a hydrogen atom or a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an i-propyl group. , Sec-butyl group, t-butyl group, t-amyl group, cyclopentyl group, cyclohexyl group and other aliphatic hydrocarbon groups, or ester groups, amides, alkyl-substituted amino groups, ether groups, thioether groups, and other heteroatoms Groups and the like.
In one embodiment of the present invention, at least one of R ₃ and R ₄ is preferably a hydrogen atom, and more preferably both are hydrogen atoms.

In the general formula (2), R ₃ and R ₄ may be connected to each other to form a ring. The ring formed is preferably a single ring, and examples thereof include cyclobutane, cyclopentane, cyclohexane, cycloheptane and the like.

Examples of the divalent linking group represented by L ₃ include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and hexane. -1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11- Diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane- A linear alkanediyl group such as a 1,17-diyl group;
Propane-1,2-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-2,2-diyl group, 1-methylbutane-1,3-diyl group, 2-methyl Branched alkanediyl groups such as propane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group Valent alicyclic saturated hydrocarbon group, etc .;
Examples include ether groups such as (poly) ethyleneoxy groups and (poly) propyleneoxy groups.
In one embodiment of the present invention, L ₃ is preferably a single bond, a methylene group, or the like.

  In one embodiment of the present invention, the acid-decomposable group represented by the general formula (2) is preferably represented by the following general formula (3).

In general formula (3),
_{L 2, L 3, R 3} , R 4, n, and X, _L 2 in general formula _{(2), L 3, R} 3, is _R 4, n, and each synonymous with X. n ₂ represents an integer of 1 or more, * represents a bonding position.

n ₂ is preferably an integer of 1 to 4, and more preferably an integer of 1 to 2.

  In one embodiment of the present invention, the resin (A) preferably contains a repeating unit having an acid-decomposable group represented by the general formula (1) or (2). As this repeating unit, for example, repeating units represented by the following general formulas (A1) and (A2) are preferable.

In general formula (A1),
R represents a hydrogen atom, an alkyl group, a fluoroalkyl group, a cyano group or a halogen atom. Here, as an alkyl group, a methyl group, an ethyl group, n-propyl group, n-butyl group, i-propyl group, sec-butyl group etc. are mentioned, for example. As a fluoroalkyl group, a part of hydrogen atoms of a perfluoroalkyl group such as a trifluoromethyl group or a pentafluoroethyl group, or an alkyl group such as CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ is substituted with a fluorine atom. And partially substituted fluoroalkyl groups.

R _{1, R 2, L} 1, X and n have the same meanings as _{R 1,} R _{2, L} 1, X and n in general formula (1).

In general formula (A2),
R represents a hydrogen atom, an alkyl group, a fluoroalkyl group, a cyano group or a halogen atom. Specific examples of the alkyl group and the fluoroalkyl group are the same as those of R in the general formula (A1).

R ₁ , R ₂ , R ₃ , R ₄ , L ₂ , L ₃ , X and n are R ₁ , R ₂ , R ₃ , R ₄ , L ₂ , L ₃ , and R in the general formula (2). Synonymous with X and n.

  Although the specific example of the repeating unit which has an acid-decomposable group represented by general formula (1) or (2) below is shown, this invention is not limited to this.

  The resin (A) may contain a repeating unit having an acid-decomposable group different from the acid-decomposable group having a crosslinkable reactive group as a protective group (hereinafter referred to as repeating unit (a-1)).

  The repeating unit (a-1) is preferably a repeating unit represented by the following general formula (AI).

In general formula (AI),
Xa ₁ represents a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH ₂ —R ₉ . Xa ₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

R ₉ represents a hydroxyl group or a monovalent organic group. Examples of the monovalent organic group include an alkyl group having 5 or less carbon atoms and an acyl group, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group.

  T represents a single bond or a divalent linking group.

Rx _{1 to} Rx ₃ each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic).

At least two of Rx _{1 to} Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

  Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.

T is preferably a single bond or a —COO—Rt— group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group or a — (CH ₂ ) ₃ — group.

The alkyl group of Rx ₁ ~Rx _3, preferably from 1 to 4 carbon atoms straight-chain or branched.

The cycloalkyl group rx ₁ to Rx _3, a monocyclic cycloalkyl group having 3 to 8 carbon atoms, a cycloalkyl group of polycyclic 7 to 20 carbon atoms preferably.

The cycloalkyl group formed by combining at least two of Rx _{1 to} Rx ₃ is preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms or a polycyclic cycloalkyl group having 7 to 20 carbon atoms. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.

An embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are combined to form the above-described cycloalkyl group is preferred.

In one embodiment, T in the general formula (AI) is a single bond, and Rx ₁ , Rx ₂ and Rx ₃ are preferably alkyl groups, and the alkyl group represented by Rx ₁ , Rx ₂ and Rx ₃ The total number of carbon atoms is more preferably 4 or more, still more preferably 5 or more, and particularly preferably 6 or more.

Although the specific example of the repeating unit (a-1) which has a preferable acid-decomposable group is shown below, this invention is not limited to this. In the formula, Xa ₁ represents any of H, CH ₃ , CF ₃ , and CH ₂ OH, and Rxa and Rxb each represents a linear or branched alkyl group having 1 to 4 carbon atoms.

  The resin (A) is more preferably a resin having a repeating unit represented by the following general formula (I).

In general formula (I),
R ₃₁ represents a hydrogen atom or a substituent.
R ₃₂ represents a substituent.
R ₃₃ represents an atomic group necessary for forming a monocyclic alicyclic hydrocarbon structure together with the carbon atom to which R ₃₂ is bonded.

  In the alicyclic hydrocarbon structure, a part of carbon atoms constituting the ring may be substituted with a hetero atom or a group having a hetero atom.

The substituent represented by R ₃₁ is preferably an alkyl group or a fluoroalkyl group. The alkyl group represented by R ₃₁ may further have a substituent (for example, a hydroxyl group).

R ₃₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

As the substituent represented by R ₃₂ , an alkyl group is preferable. R ₃₂ is more preferably an alkyl group having 3 to 10 carbon atoms, and further preferably an alkyl group having 4 to 7 carbon atoms.

R ₃₂ is, for example, a methyl group, an ethyl group, an isopropyl group, or a t-butyl group, preferably an isopropyl group or a t-butyl group, and more preferably a t-butyl group.

The monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with the carbon atom is preferably a 3- to 8-membered ring, and more preferably a 5- or 6-membered ring.

In the monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with the carbon atom, examples of the hetero atom that can substitute a part of the carbon atoms constituting the ring include an oxygen atom and a sulfur atom. Examples of the carbonyl group include a carbonyl group. However, the group having a hetero atom is preferably not an ester group (ester bond).

The monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with the carbon atom is preferably formed only from the carbon atom and the hydrogen atom.

  The repeating unit represented by the general formula (I) is preferably a repeating unit represented by the following general formula (4).

In general formula (4),
R ₄₁ represents a hydrogen atom or a substituent, R ₄₂ represents a substituent, and n ₄ represents an integer of 1 or more.

In the general formula _{(4), R 41} and _{R 42} are each the same meaning as _{R 31} and _{R 32} in the general formula (I).
n ₄ is preferably an integer of 1 to 4, and more preferably 1 or 2.

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

  As for the repeating unit (a-1) having an acid-decomposable group that can be contained in the resin (A), one type may be used, or two or more types may be used in combination.

  Moreover, resin (A) may contain the repeating unit which decomposes | disassembles by the effect | action of an acid and generate | occur | produces an alcoholic hydroxyl group as an acid-decomposable repeating unit (a-1). For example, you may use together with the repeating unit represented by general formula (AI). The following specific examples are given as one form of the repeating unit that decomposes by the action of an acid to generate an alcoholic hydroxy group.

<Repeating unit having a crosslinkable reactive group>
When the resin (A) does not contain a repeating unit having an acid-decomposable group containing a crosslinkable reactive group in the protective group, the resin (A) contains the above-mentioned repeating unit (a-1) and is crosslinkable. It is preferable to further include a repeating unit (a-2) having a reactive group.

  The repeating unit (a-2) having a crosslinkable reactive group may be any repeating unit having the above-described crosslinkable reactive group.

  The repeating unit (a-2) having a crosslinkable reactive group is preferably, for example, a repeating unit represented by the following general formula (a-2-1).

In formula, L < ₁ >, X is synonymous with L < ₁ >, X in General formula (1) mentioned above, respectively.

  In addition, the resin (A) has a hydroxyl group or a cyano group as the repeating unit (a-2) having a crosslinkable reactive group, other than the general formulas (A1), (A2), general formulas (AI), and (AII) May have a repeating unit. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no acid-decomposable group. Examples of the repeating unit having these structures include repeating units represented by the following general formulas (AIIa) to (AIId).

In the general formulas (AIIa) to (AIId),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

R ₂ c to R ₄ c each independently represents a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the remaining is a hydrogen atom. More preferably, _two of R ₂ c to R ₄ c are hydroxyl groups and the rest are hydrogen atoms.

  The content of the repeating unit having a hydroxyl group or a cyano group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, still more preferably from 10 to 25 mol%, based on all repeating units in the resin (A).

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

  The resin (A) preferably has a repeating unit having an acid group. Examples of the acid group include a carboxy group, a sulfonamide group, a sulfonylimide group, a bisulsulfonylimide group, and an aliphatic alcohol (for example, hexafluoroisopropanol group) substituted with an electron-withdrawing group at the α-position. More preferably it has units. By containing the repeating unit having an acid group, the resolution in the contact hole application is increased. The repeating unit having an acid group includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an acid group in the main chain of the resin through a linking group. Either a repeating unit bonded, or a polymerization initiator or chain transfer agent having an acid group is introduced at the end of the polymer chain at the time of polymerization, both of which are preferable, and the linking group is a monocyclic or polycyclic hydrocarbon structure You may have. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

  As for the content rate of the repeating unit which has an acid group, 0-20 mol% is preferable with respect to all the repeating units in resin (A), More preferably, it is 3-15 mol%, More preferably, it is 5-10 mol%.

Specific examples of the repeating unit having an acid group are shown below, but the present invention is not limited thereto. In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  Moreover, resin (A) may contain the following repeating unit as a repeating unit (a-2) which has a crosslinkable reactive group.

  The content of the repeating unit having an acid-decomposable group having a crosslinkable reactive group in the protective group in the resin (A) is 5 to 80 mol% with respect to all the repeating units in the resin (A). Preferably, it is 35 to 70 mol%, more preferably 50 to 65 mol%.

  When the resin (A) does not contain a repeating unit having an acid-decomposable group containing a crosslinkable reactive group in the protective group, as described above, the resin (A) has a repeating unit (a-1) and a crosslinkable reactive group. It is preferable that a repeating unit (a-2) is included. In that case, the content of the repeating unit (a-1) is preferably 5 to 80 mol%, more preferably 35 to 70 mol%, based on all repeating units in the resin (A). 50 to 65 mol% is more preferable. Moreover, it is preferable that the content rate of the repeating unit (a-2) which has a crosslinkable reactive group is 1-40 mol% with respect to all the repeating units in resin (A), and is 1-20 mol%. More preferably, it is more preferably 1 to 10 mol%.

<Repeating unit having at least one group selected from lactone group, hydroxyl group, cyano group and alkali-soluble group>
The resin (A) preferably further has a repeating unit having at least one group selected from a lactone group, a sultone group, a hydroxyl group, a cyano group, and an alkali-soluble group.

The repeating unit having a lactone group or a sultone group that can be contained in the resin (A) will be described.
As the lactone group or sultone group, any one having a lactone structure or sultone structure can be used, but preferably a 5- to 7-membered ring lactone structure or a sultone structure, and a 5- to 7-membered ring lactone structure or Those in which other ring structures are condensed in a form that forms a bicyclo structure or a spiro structure in the sultone structure are preferred. A repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17), or a sultone structure represented by the following general formula (SL1-1) or (SL1-2): More preferably.
A lactone structure or a sultone structure may be directly bonded to the main chain. Preferable lactone structures include (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), and (LC1-17). By using a specific lactone structure or sultone structure, development defects are improved.

The lactone structure part or sultone structure part may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, the plural substituents (Rb ₂ ) may be the same or different, and the plural substituents (Rb ₂ ) may be bonded to form a ring. .

  As a repeating unit having a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-17) and a sultone structure represented by the general formula (SL1-1) or (SL1-2) And repeating units represented by the following general formula (AII).

In general formula (AII),
Rb ₀ represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group represented by Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether bond, an ester bond, a carbonyl group, or a divalent linking group obtained by combining these. Preferably a single bond, -Ab ₁ -CO ₂ - is a divalent linking group represented by.

Ab ₁ is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.

  V represents a group having a structure represented by any of general formulas (LC1-1) to (LC1-17), general formulas (SL1-1), and (SL1-2).

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

  The content of the repeating unit having a lactone group or a sultone group is preferably from 15 to 60 mol%, more preferably from 20 to 50 mol%, still more preferably from 30 to 50 mol%, based on all repeating units in the resin (A). .

  Examples of the repeating unit having a lactone group or a sultone group include the following repeating units. By selecting an optimal lactone group, the pattern profile and the density dependence become good.

  Two or more repeating units having a lactone structure or a sultone structure can be used in combination.

<Repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability>
The resin (A) may further have a repeating unit that has an alicyclic hydrocarbon structure and does not exhibit acid decomposability. This can reduce the elution of low molecular components from the actinic ray-sensitive or radiation-sensitive film into the immersion liquid during immersion exposure. Examples of such a repeating unit include 1-adamantyl (meth) acrylate, diamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and cyclohexyl (meth) acrylate repeating units.

<Repeating unit having neither hydroxyl group nor cyano group>
It is preferable that the resin (A) of the present invention further contains a repeating unit represented by the general formula (IV) that has neither a hydroxyl group nor a cyano group.

In general formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.

Ra represents a hydrogen atom, an alkyl group, or a —CH ₂ —O—Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or an acyl group.

The cyclic structure possessed by R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms (more preferably 3 to 7 carbon atoms) and a cycloalkenyl group having 3 to 12 carbon atoms.

  The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. As the bridged cyclic hydrocarbon ring, a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, a tetracyclic ring Examples include hydrocarbon rings. The bridged cyclic hydrocarbon ring also includes, for example, a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed.

Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 ^2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

  These alicyclic hydrocarbon groups may have a substituent, and preferred substituents include a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, an amino group protected with a protecting group, and the like. It is done.

  The content of the repeating unit represented by the general formula (IV) having neither a hydroxyl group nor a cyano group is preferably from 0 to 40 mol%, more preferably based on all repeating units in the resin (A). 0 to 20 mol%.

Specific examples of the repeating unit represented by the general formula (IV) are listed below, but the present invention is not limited to these. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

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

In general formula (nI) and general formula (nII),
R ₁₃ ′ to R ₁₆ ′ each independently have a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, or a lactone structure. Represents a group or a group having an acid-decomposable group.

X ₁ and X ₂ each independently represents a methylene group, an ethylene group, an oxygen atom or a sulfur atom.

  n represents an integer of 0 to 2.

Examples of the acid-decomposable group in the group having an acid-decomposable group as R ₁₃ ′ to R ₁₆ ′ include cumyl ester group, enol ester group, acetal ester group, tertiary alkyl ester group, etc. A tertiary alkyl ester group represented by —C (═O) —O—R ₀ is preferred. In the formula, R ₀ is a tertiary alkyl group such as a t-butyl group or a t-amyl group.

  Resin (A) adjusts dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc., which are general required characteristics of resist, in addition to the above repeating structural units. For this purpose, various repeating structural units can be included.

  Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.

  As a result, the performance required for the resin (A), in particular, (1) solubility in coating solvents, (2) film-formability (glass transition point), (3) alkali developability, (4) film slip (hydrophobic / hydrophobic) (Selection of alkali-soluble group), (5) adhesion of the unexposed part to the substrate, (6) dry etching resistance, etc. can be finely adjusted.

  As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.

  In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized. For example, as described in JP 2013-218223 A, paragraph 0029 to paragraph 0076, a repeating unit containing a basic structural moiety, or the [0045] formula (1a-) of WO 2011/122336 A repeating unit having a cyclic carbonate structure described as 7) may be copolymerized.

  In the resin (A), the molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and the general required performance of the resist, resolving power, heat resistance, sensitivity. It is set appropriately in order to adjust etc.

  When the composition of the present invention is for ArF exposure, the resin (A) preferably has no aromatic group from the viewpoint of transparency to ArF light. Moreover, it is preferable that resin (A) does not contain a fluorine atom and a silicon atom from a compatible viewpoint with the hydrophobic resin mentioned later.

  The resin (A) is preferably one in which all of the repeating units are composed of (meth) acrylate-based repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units. Although it can be used, the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units.

  The resin (A) can be synthesized according to a conventional method such as radical polymerization, anionic polymerization, cationic polymerization, or living radical polymerization. In the polymerization, a chain transfer agent or the like known in the field of polymer polymerization may be used. In addition, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and polymerization is performed by heating, a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass.
The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 60-100 ° C.

  After completion of the reaction, the mixture is allowed to cool to room temperature and purified. Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. , Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent A normal method such as a method can be applied.

  For example, the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times that of the reaction solution. It is preferable to remove residual monomers and oligomer components as much as possible by such a method.

  The solvent used for the precipitation or reprecipitation operation from the polymer solution (precipitation or reprecipitation solvent) may be any poor solvent for this polymer. Depending on the type of polymer, hydrocarbon, halogenated hydrocarbon, nitro A compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, a mixed solvent containing these solvents, and the like can be appropriately selected for use. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol) or water is preferable.

  The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300-1000 mass parts.

  The temperature for precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.

The precipitated or re-precipitated polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure.
Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).

  In addition, after depositing and separating the resin once, it may be dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent. That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is contacted, the resin is precipitated (step a), the resin is separated from the solution (step b), and the resin solution A is dissolved again in the solvent. Preparation (step c), and then contacting the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably not more than 5 times the volume amount). It may be a method including depositing a solid (step d) and separating the deposited resin (step e).

  In order to prevent the resin from aggregating after the preparation of the composition, for example, as described in JP-A-2009-037108, the synthesized resin is dissolved in a solvent to form a solution. A step of heating at about 30 ° C. to 90 ° C. for about 30 minutes to 4 hours may be added.

  The weight average molecular weight of the resin (A) of the present invention is preferably 1,000 to 200,000, more preferably 1,000 to 20,000, and most preferably 1,000 as a polystyrene conversion value by GPC method. ~ 15,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.

The degree of dispersion (molecular weight distribution) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, particularly preferably 1.2 to 2.0. . The smaller the degree of dispersion, the better the resolution and the resist shape, the smoother the side wall of the resist pattern, and the better the roughness.
The weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) of the resin were measured by GPC (solvent: tetrahydrofuran, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40). (° C., flow rate: 1.0 mL / min, detector: RI).

  In the composition of the present invention, the blending amount of the resin (A) in the whole composition is preferably 50 to 99% by mass, more preferably 60 to 95% by mass in the total solid content.

  In the present invention, the resin (A) may be used alone or in combination. In addition, a resin corresponding to the resin (A) and a resin that does not correspond to the resin (A) and decomposes by the action of an acid may be used in combination. In this case, it is preferable that the resin corresponding to the resin (A) is 50% by mass or more based on the total amount of the resin.

[Compound capable of generating acid upon irradiation with actinic ray or radiation (B)]
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a compound (“photoacid generator” or “compound (B)”) that generates an acid upon irradiation with actinic rays or radiation.

  Examples of such photoacid generators include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, actinic rays used in microresists, etc. Known compounds that generate an acid upon irradiation with radiation and mixtures thereof can be appropriately selected and used.

  Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

  Further, a group that generates an acid upon irradiation with these actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the polymer, such as US Pat. No. 3,849,137, German Patent No. No. 3914407, JP-A 63-26653, JP-A 55-164824, JP-A 62-69263, JP-A 63-146038, JP-A 63-163452, The compounds described in JP-A-62-153853 and JP-A-63-146029 can be used.

  Furthermore, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712, etc. can also be used.

  Among the compounds that decompose upon irradiation with actinic rays or radiation to generate an acid, compounds represented by the following general formulas (ZI), (ZII), and (ZIII) can be exemplified.

In the above general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.

X ⁻ represents a non-nucleophilic anion, preferably sulfonate anion, carboxylate anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) methide anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ^{− and the} like. Preferably, it is an organic anion containing a carbon atom.

  Preferable organic anions include organic anions represented by the following formula.

Where
Rc ₁ represents an organic group.

Examples of the organic group in Rc ₁ include those having 1 to 30 carbon atoms, and preferably an alkyl group, an aryl group, or a plurality thereof, which may be substituted, is a single bond, —O—, —CO ₂ —, — Examples include groups linked by a linking group such as S-, -SO _3- , -SO ₂ N (Rd ₁ )-. Rd ₁ represents a hydrogen atom or an alkyl group.

Rc ₃ , Rc ₄ and Rc ₅ each independently represents an organic group. Preferred examples of the organic group for Rc ₃ , Rc ₄ , and Rc ₅ include the same organic groups as those for Rc _1, and a perfluoroalkyl group having 1 to 4 carbon atoms is most preferred.

Rc ₃ and Rc ₄ may combine to form a ring. Examples of the group formed by combining Rc ₃ and Rc ₄ include an alkylene group and an arylene group. Preferably, it is a C2-C4 perfluoroalkylene group.

The organic group of Rc ₁ and Rc _{3 to} Rc ₅ is particularly preferably an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved. Further, when Rc ₃ and Rc ₄ are combined to form a ring, the acidity of the acid generated by light irradiation is increased, and the sensitivity is improved.

The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.

Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).

Specific examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include corresponding groups in the compounds (ZI-1), (ZI-2) and (ZI-3) described later.

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, the general formula at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by (ZI) is, at least one bond with structure of R ₂₀₁ to R ₂₀₃ of another compound represented by formula (ZI) It may be a compound.

  More preferable (ZI) components include compounds (ZI-1), (ZI-2), and (ZI-3) described below.

The compound (ZI-1) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZI), arylsulfonium compound, i.e., a compound having arylsulfonium as a cation.

In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.

  Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

  The aryl group of the arylsulfonium compound is preferably an aryl group such as a phenyl group or a naphthyl group, or a heteroaryl group such as an indole residue or a pyrrole residue, more preferably a phenyl group or an indole residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

  The alkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, sec- Examples thereof include a butyl group and a t-butyl group.

  The cycloalkyl group that the arylsulfonium compound has as necessary is preferably a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

Aryl group, alkyl group of R ₂₀₁ to R _203, cycloalkyl group, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms) , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, and particularly preferable. Is an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of the three R _{201 to} R ₂₀₃ , or may be substituted with all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (ZI-2) will be described. Compound (ZI-2) is a compound in the case where R _{201 to} R ₂₀₃ in formula (ZI) each independently represents an organic group containing no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.

The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear, branched, cyclic 2-oxoalkyl group, or an alkoxycarbonylmethyl group, particularly preferably Is a linear, branched 2-oxoalkyl group.

The alkyl group as R ₂₀₁ to R ₂₀₃ may be linear, it may be either branched, preferably a straight-chain or branched alkyl group (e.g., methyl group having 1 to 10 carbon atoms, an ethyl group, a propyl Group, butyl group, pentyl group). The alkyl group as R ₂₀₁ to R ₂₀₃ is a straight-chain or branched 2-oxoalkyl group is preferably an alkoxycarbonyl methyl group.

The cycloalkyl group as R ₂₀₁ to R ₂₀₃ is preferably, and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, norbornyl).
The cycloalkyl group as R ₂₀₁ to R ₂₀₃ is preferably a cyclic 2-oxoalkyl group.

Linear as R ₂₀₁ to R _203, branched or cyclic 2-oxoalkyl group may preferably be a group having a 2-position> C = O in the above-described alkyl or cycloalkyl group.

The alkoxy group in the alkoxycarbonylmethyl group as R ₂₀₁ to R _203, preferably may be mentioned alkoxy groups having 1 to 5 carbon atoms (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group).

R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

  The compound (ZI-3) is a compound represented by the following general formula (ZI-3), and is a compound having a phenacylsulfonium salt structure.

In general formula (ZI-3),
R _{1c to} R _5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a halogen atom.

R _6c and R _7c each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.

  Rx and Ry each independently represents an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group.

Any two or more of R _1c to R _7c, and R _x and R _y may be bonded to each other to form a ring structure, the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond May be included. Examples of the group formed by combining any two or more of R _{1c to} R _7c and R _x and R _y include a butylene group and a pentylene group.

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

The alkyl group as R _{1c to} R _7c may be either linear or branched, for example, a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. Or a linear or branched alkyl group (for example, a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, or a linear or branched pentyl group).

The cycloalkyl group as R _{1c to} R _7c is preferably a cycloalkyl group having 3 to 8 carbon atoms (for example, a cyclopentyl group or a cyclohexyl group).

The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (For example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), C3-C8 cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) ).

Preferably, any one of R _{1c to} R _5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably the sum of the carbon number of R _{1c to} R _5c is 2 ~ 15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.

_Examples of the alkyl group as R _x and R _y include the same alkyl groups as R _{1c to} R _7c . The alkyl group as R _x and R _y is preferably a linear or branched 2-oxoalkyl group or an alkoxycarbonylmethyl group.

The cycloalkyl group as R _x and R _y may be the same as the cycloalkyl group as R _1c to R _7c. The cycloalkyl group as R _x and R _y is preferably a cyclic 2-oxoalkyl group.

Examples of the linear, branched, or cyclic 2-oxoalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R _{1c to} R _7c .

Examples of the alkoxy group in the alkoxycarbonylmethyl group include the same alkoxy groups as R _{1c to} R _5c .

R _x and R _y are preferably an alkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more.

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

Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _207, more preferably a phenyl group.

The alkyl group as R ₂₀₄ to R ₂₀₇ may be linear, it may be either branched, preferably a straight-chain or branched alkyl group (e.g., methyl group having 1 to 10 carbon atoms, an ethyl group, a propyl Group, butyl group, pentyl group).

The cycloalkyl group as R ₂₀₄ to R ₂₀₇ is preferably, and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, norbornyl).

R ₂₀₄ to R ₂₀₇ may have a substituent. The R ₂₀₄ to R ₂₀₇ are substituents which may have, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (e.g., 6 carbon atoms 15), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups and the like.

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

  Among the compounds that generate an acid upon irradiation with actinic rays or radiation, compounds represented by the following general formulas (ZIV), (ZV), and (ZVI) can be further exemplified.

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.

R ₂₂₆ represents an alkyl group or an aryl group.

R ₂₂₇ and R ₂₂₈ each independently represents an alkyl group, an aryl group, or an electron-withdrawing group.
R ₂₂₇ is preferably an aryl group.

R ₂₂₈ is preferably an electron-withdrawing group, more preferably a cyano group or a fluoroalkyl group.

  A represents an alkylene group, an alkenylene group or an arylene group.

  As the compound that generates an acid upon irradiation with actinic rays or radiation, compounds represented by general formulas (ZI) to (ZIII) are preferable.

  The compound (B) is preferably a compound that generates an aliphatic sulfonic acid having a fluorine atom or a benzenesulfonic acid having a fluorine atom upon irradiation with actinic rays or radiation.

  The compound (B) preferably has a triphenylsulfonium structure.

  The compound (B) is preferably a triphenylsulfonium salt compound having an alkyl group or a cycloalkyl group not substituted with fluorine in the cation moiety.

  Among the compounds that generate an acid upon irradiation with actinic rays or radiation, examples of particularly preferable compounds are listed below.

  A photo-acid generator can be used individually by 1 type or in combination of 2 or more types. When two or more types are used in combination, it is preferable to combine two types of compounds that generate two types of organic acids that differ in the total number of atoms excluding hydrogen atoms by two or more.

  The content of the photoacid generator is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. Preferably it is 1-7 mass%. By making the content rate of a photo-acid generator into this range, the exposure margin at the time of forming a resist pattern and the crosslinking reactivity with a crosslinked layer forming material improve.

[Crosslinking agent]
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain a compound (C) having an acid crosslinkable group (hereinafter also referred to as “compound (C)” or “crosslinking agent”). The compound (C) is preferably a compound containing two or more hydroxymethyl groups or alkoxymethyl groups in the molecule. Moreover, it is preferable that the compound (C) contains the methylol group from a viewpoint of LER (Line Edge Roughness) (an improvement.

First, the case where the compound (C) is a low molecular compound will be described (hereinafter referred to as the compound (C ′)). The compound (C ′) is preferably a hydroxymethylated or alkoxymethylated phenol compound, an alkoxymethylated melamine compound, an alkoxymethylglycoluril compound, and an alkoxymethylated urea compound. Particularly preferred compounds (C ′) include phenol derivatives and alkoxymethyl glycols containing 3 to 5 benzene rings in the molecule, and further having two or more hydroxymethyl groups or alkoxymethyl groups, and a molecular weight of 1200 or less. Examples include uril derivatives.
As the alkoxymethyl group, a methoxymethyl group and an ethoxymethyl group are preferable.

  Among the examples of the compound (C ′), a phenol derivative having a hydroxymethyl group can be obtained by reacting a corresponding phenol compound having no hydroxymethyl group with formaldehyde under a base catalyst. A phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst.

  Examples of another preferable compound (C ′) further have an N-hydroxymethyl group or an N-alkoxymethyl group such as alkoxymethylated melamine compounds, alkoxymethylglycoluril compounds, and alkoxymethylated urea compounds. A compound can be mentioned.

Examples of such compounds include hexamethoxymethyl melamine, hexaethoxymethyl melamine, tetramethoxymethyl glycoluril, 1,3-bismethoxymethyl-4,5-bismethoxyethylene urea, bismethoxymethyl urea, and the like. 133, 216A, West German Patent 3,634,671, 3,711,264, EP 0,212,482A.
Of the specific examples of the compound (C ′), those particularly preferred are listed below.

In the formula, L1 to L8 each independently represent a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, or an alkyl group having 1 to 6 carbon atoms.
In the present invention, the content of the compound (C ′) is preferably 3 to 65% by mass, more preferably 5 to 50% by mass in the total solid content of the negative resist composition. By making the content rate of a compound (C ') into the range of 3-65 mass%, while maintaining that the remaining film rate and resolving power fall, the stability at the time of the preservation | save of the composition of this invention is kept favorable. be able to.

In the present invention, the compound (C ′) may be used alone or in combination of two or more. From the viewpoint of a good pattern shape, it is preferable to use a combination of two or more.
For example, in addition to the above-described phenol derivative, in the case where another compound (C ′), for example, the above-described compound having an N-alkoxymethyl group is used in combination, the ratio of the above-described phenol derivative to the other compound (C ′) is The molar ratio is usually 90/10 to 20/80, preferably 85/15 to 40/60, more preferably 80/20 to 50/50.

  The compound (C) containing an acid-crosslinkable group may be in the form of a resin containing a repeating unit having an acid-crosslinkable group (hereinafter also referred to as compound (C ″)). Since the molecular unit of the unit contains a cross-linking group, the cross-linking reactivity is higher than that of a normal resin + cross-linking agent system, so that a hard film can be formed, acid diffusibility and dry etching resistance. As a result, the diffusibility of the acid in the exposed portion of actinic rays or radiation such as electron beams and extreme ultraviolet rays is greatly suppressed, so that the resolution, pattern shape and LER in a fine pattern are excellent. In addition, when the reaction point of the resin and the reaction point of the crosslinking group are close to each other as in the repeating unit represented by the following general formula (1), the composition has an improved sensitivity during pattern formation.

Examples of the compound (C ″) include a resin containing a repeating unit represented by the following general formula (1). The repeating unit represented by the general formula (1) may have a substituent. It is a structure containing at least one good methylol group.
Here, the “methylol group” is a group represented by the following general formula (M), and in one embodiment of the present invention, a hydroxymethyl group or an alkoxymethyl group is preferable.

In the formula, R2, R3 and Z are as defined in the general formula (1) described later.
First, general formula (1) will be described.

In general formula (1),
R ₁ represents a hydrogen atom, a methyl group, or a halogen atom.
R ₂ and R ₃ represent a hydrogen atom, an alkyl group, or a cycloalkyl group.
L represents a divalent linking group or a single bond.
Y represents a substituent other than a methylol group.
Z represents a hydrogen atom or a substituent.
m represents an integer of 0 to 4.
n represents an integer of 1 to 5.
m + n is 5 or less.
When m is 2 or more, the plurality of Y may be the same as or different from each other.
When n is 2 or more, the plurality of R2, R3 and Z may be the same as or different from each other.
Two or more of Y, R ₂ , R ₃ and Z may be bonded to each other to form a ring structure.

R ₁ , R ₂ , R ₃ , L and Y may each have a substituent.

When m is 2 or more, a plurality of Y may be bonded to each other through a single bond or a linking group to form a ring structure.
Moreover, the repeating unit represented by the general formula (1) is preferably represented by the following general formula (2) or (3).

In general formulas (2) and (3),
R ₁ , R ₂ , R ₃ , Y, Z, m and n are as defined in the general formula (1).
Ar represents an aromatic ring.
W ₁ and W ₂ represent a divalent linking group or a single bond.

  The repeating unit represented by the general formula (1) is more preferably represented by the following general formula (2 ') or (3').

R ₁ , Y, Z, m and n in the general formulas (2 ′) and (3 ′) have the same meanings as the groups in the general formula (1). Ar in the general formula (2 ′) has the same meaning as Ar in the general formula (2).
In the general formula (3 ′), W ₃ is a divalent linking group.

In the said general formula (2 ') and (3'), f is an integer of 0-6.
In the general formulas (2 ′) and (3 ′), g is 0 or 1.

  The general formula (2 ′) is particularly preferably represented by any one of the following general formulas (1-a) to (1-c). The compound (C ″) particularly preferably contains a repeating unit represented by any one of the following general formulas (1-a) to (1-c) or a repeating unit represented by the above general formula (3 ′). .

R ₁ , Y and Z in the general formulas (1-a) to (1-c) have the same meanings as the groups in the general formula (1).
In the general formulas (1-b) to (1-c),
Y ″ represents a hydrogen atom or a monovalent substituent. However, Y ″ may be a methylol group.
R ₄ represents a hydrogen atom or a monovalent substituent.
f represents an integer of 1 to 6.
m is 0 or 1, and n represents an integer of 1 to 3.

The content of the repeating unit having an acid-crosslinkable group in the compound (C ″) is preferably 3 to 40 mol%, more preferably 5 to 30 mol%, based on all the repeating units of the compound (C ″). It is more preferable.
The content of the compound (C ″) is preferably 5 to 50% by mass and more preferably 10 to 40% by mass in the total solid content of the negative resist composition.

The compound (C ″) may contain two or more repeating units having an acid crosslinkable group, or two or more compounds (C ″) may be used in combination. Further, the compound (C ′) and the compound (C ″) can be used in combination.
Specific examples of the repeating unit having an acid crosslinkable group contained in the compound (C ″) include the following structures.

[solvent]
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain a solvent. Solvents that can be used when preparing the actinic ray-sensitive or radiation-sensitive resin composition by dissolving the above components include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate Examples include organic solvents such as esters, alkyl alkoxypropionates, cyclic lactones having 4 to 10 carbon atoms, monoketone compounds having 4 to 10 carbon atoms, which may contain rings, alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates. Can do.

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

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

  Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.

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

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

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

  Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.

  Examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-acetate. 2-propyl is preferred.

  Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

  As a solvent which can be preferably used, a solvent having a boiling point of 130 ° C. or higher under normal temperature and normal pressure can be mentioned. Specifically, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, acetic acid -2- (2-ethoxyethoxy) ethyl and propylene carbonate are mentioned. Butyl butanoate, isoamyl acetate, methyl 2-hydroxyisobutyrate may be used as a solvent.

  In the present invention, the above solvents may be used alone or in combination of two or more.

  In this invention, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group as an organic solvent.

  Examples of the solvent containing a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate, and the like. Particularly preferred are propylene glycol monomethyl ether and ethyl lactate.

  Examples of the solvent not containing a hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide and the like. Among these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, and butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate. 2-heptanone is most preferred.

  The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.

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

[Basic compounds]
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a basic compound in order to reduce changes in performance over time from exposure to heating.

  Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).

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

  About the said alkyl group, as an alkyl group which has a substituent, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.

R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.

  The alkyl groups in these general formulas (A) to (E) are more preferably unsubstituted.

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

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

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

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

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

[Hydrophobic resin]
The composition of the present invention may contain a hydrophobic resin. The hydrophobic resin is preferably different from the resin (A).

  Hydrophobic resins are preferably designed to be unevenly distributed at the interface, but unlike surfactants, they do not necessarily have hydrophilic groups in the molecule and contribute to uniform mixing of polar / nonpolar substances. You don't have to.

  Effects of adding a hydrophobic resin include control of static / dynamic contact angle of actinic ray-sensitive or radiation-sensitive film surface to water, improvement of immersion liquid tracking, suppression of outgas, etc. Can do. Outgas suppression is particularly required when exposure is performed with EUV light.

The hydrophobic resin has at least one of “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer. It is preferable to have two or more types.

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

  When the hydrophobic resin contains a fluorine atom, it may be a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom. preferable.

  The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and further a fluorine atom It may have a substituent other than.

  The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.

  Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom. .

  Preferred examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom include groups represented by the following general formulas (F2) to (F4). The invention is not limited to this.

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group (straight or branched). Provided that at least one of R _{57 to} R ₆₁ , at least one of R _{62 to} R ₆₄ , and at least one of R _{65 to} R ₆₈ are each independently a fluorine atom or at least one hydrogen atom is a fluorine atom. It represents a substituted alkyl group (preferably having 1 to 4 carbon atoms).

R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

  Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.

  Specific examples of the group represented by the general formula (F3) include those exemplified in US2012 / 0251948A1 [0500].

Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, -CH _(CF 3) OH and the like, -C _{(CF 3)} 2 OH is preferred.

  The partial structure containing a fluorine atom may be directly bonded to the main chain, and further from the group consisting of an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond and a ureylene bond. You may couple | bond with a principal chain through the group selected or the group which combined these 2 or more.

  The hydrophobic resin may contain a silicon atom. The partial structure having a silicon atom is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.

  Examples of the alkylsilyl structure or the cyclic siloxane structure include partial structures described in paragraphs [0304] to [0307] of JP2013-178370A.

  Examples of the repeating unit having a fluorine atom or a silicon atom include those exemplified in US2012 / 0251948A1 [0519].

Further, as described above, the hydrophobic resin preferably includes a CH ₃ partial structure in the side chain portion.

Here, the CH ₃ partial structure of the side chain portion in the hydrophobic resin (hereinafter also simply referred to as “side chain CH ₃ partial structure”) includes a CH ₃ partial structure of an ethyl group, a propyl group, or the like. Is.

On the other hand, methyl groups directly bonded to the main chain of the hydrophobic resin (for example, α-methyl groups of repeating units having a methacrylic acid structure) contribute to the uneven distribution of the surface of the hydrophobic resin due to the influence of the main chain. Since it is small, it is not included in the CH ₃ partial structure in the present invention.

More specifically, when the hydrophobic resin includes a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M). a _is, if R 11 _{to R 14} is CH ₃ "itself", the CH ₃ is not included in the CH ₃ partial structure contained in the side chain portion in the present invention.

Meanwhile, CH ₃ partial structure exists through some atoms from C-C backbone, and those falling under CH ₃ partial structures in the present invention. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it is assumed that it has “one” CH ₃ partial structure in the present invention.

In the general formula (M),
R < ₁₁ > -R < ₁₄ > represents a side chain part each independently.

Examples of R _{11 to} R _{14 in the} side chain portion include a hydrogen atom and a monovalent organic group.

Examples of the monovalent organic group for R _{11 to} R ₁₄ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylaminocarbonyl. Group, an arylaminocarbonyl group, and the like, and these groups may further have a substituent.

The hydrophobic resin is preferably a resin having a repeating unit having a CH ₃ partial structure in the side chain portion. As such a repeating unit, the repeating unit represented by the following general formula (II) and the following general unit It is more preferable to have at least one repeating unit (x) among the repeating units represented by the formula (III).
Hereinafter, the repeating unit represented by formula (II) will be described in detail.

In the general formula (II), X _b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, R ₂ has one or more CH ₃ partial structure represents a stable organic radical to acid. Here, the organic group that is stable to acid is more preferably an organic group that does not have the “acid-decomposable group” described in the resin (A).

The alkyl group of _Xb1 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is preferable.

X _b1 is preferably a hydrogen atom or a methyl group.

Examples of R ₂ include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group having one or more CH ₃ partial structures. The above cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group and aralkyl group may further have an alkyl group as a substituent.

R ₂ is preferably an alkyl group or an alkyl-substituted cycloalkyl group having one or more CH ₃ partial structures.

The acid-stable organic group having one or more CH ₃ partial structures as R ₂ preferably has 2 or more and 10 or less CH ₃ partial structures, and more preferably 2 or more and 8 or less.

  Preferred specific examples of the repeating unit represented by the general formula (II) are shown below. Note that the present invention is not limited to this.

  The repeating unit represented by the general formula (II) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.

In the case where the hydrophobic resin contains a CH ₃ partial structure in the side chain portion, and particularly when it does not have a fluorine atom and a silicon atom, the repeating unit represented by the general formula (II) and the general formula ( The content of at least one repeating unit (x) among the repeating units represented by III) is preferably 90 mol% or more, more preferably 95 mol% or more, based on all repeating units of the hydrophobic resin. It is more preferable. Content is 100 mol% or less normally with respect to all the repeating units of hydrophobic resin.

  The hydrophobic resin contains at least one repeating unit (x) among the repeating units represented by the general formula (II) and the repeating unit represented by the general formula (III) as all repeating units of the hydrophobic resin. On the other hand, the surface free energy of hydrophobic resin increases by containing 90 mol% or more. As a result, the hydrophobic resin is less likely to be unevenly distributed on the surface of the actinic ray-sensitive or radiation-sensitive membrane, and the static / dynamic contact angle of the actinic ray-sensitive or radiation-sensitive membrane with respect to water is reliably improved. In addition, it is possible to improve the followability of the immersion liquid.

In addition, the hydrophobic resin includes the following groups (x) to (z) both when (i) a fluorine atom and / or a silicon atom are included, and (ii) when a side chain portion includes a CH ₃ partial structure. It may have at least one group selected from

(X) an acid group,
(Y) a group having a lactone structure, an acid anhydride group, or an acid imide group,
(Z) A group capable of decomposing by the action of an acid As the acid group (x), a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) ) Methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkyl) A carbonyl) methylene group, a tris (alkylsulfonyl) methylene group, and the like.

  Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (alkylcarbonyl) methylene groups.

  The repeating unit having an acid group (x) includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a resin having a linking group. Examples include a repeating unit in which an acid group is bonded to the main chain, and a polymerization initiator or chain transfer agent having an acid group can be introduced at the end of the polymer chain at the time of polymerization. preferable. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.

  The content of the repeating unit having an acid group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 20 mol%, based on all repeating units in the hydrophobic resin. It is.

  As the group having a lactone structure, the acid anhydride group, or the acid imide group (y), a group having a lactone structure is particularly preferable.

  The repeating unit containing these groups is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid ester. Alternatively, this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent which has this group at the time of superposition | polymerization.

  Examples of the repeating unit having a group having a lactone structure include those similar to the repeating unit having a lactone structure described above in the section of the resin (A).

  The content of the repeating unit having a group having a lactone structure, an acid anhydride group, or an acid imide group is preferably 1 to 100 mol% based on all repeating units in the hydrophobic resin, and preferably 3 to 98. It is more preferable that it is mol%, and it is still more preferable that it is 5-95 mol%.

  Examples of the repeating unit having a group (z) that is decomposed by the action of an acid in the hydrophobic resin include the same repeating units having an acid-decomposable group as mentioned for the resin (A). The repeating unit having a group (z) that decomposes by the action of an acid may have at least one of a fluorine atom and a silicon atom. In the hydrophobic resin, the content of the repeating unit having a group (z) that decomposes by the action of an acid is preferably 1 to 80 mol%, more preferably 10 to 10%, based on all repeating units in the hydrophobic resin. It is 80 mol%, More preferably, it is 20-60 mol%.

  When the hydrophobic resin has a fluorine atom, the content of the fluorine atom is preferably 5 to 80% by mass and more preferably 10 to 80% by mass with respect to the weight average molecular weight of the hydrophobic resin. Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mol% in all the repeating units contained in hydrophobic resin, and it is more preferable that it is 30-100 mol%.

  When the hydrophobic resin has a silicon atom, the content of the silicon atom is preferably 2 to 50% by mass and more preferably 2 to 30% by mass with respect to the weight average molecular weight of the hydrophobic resin. Moreover, it is preferable that it is 10-100 mol% in the repeating unit containing a silicon atom in all the repeating units contained in hydrophobic resin, and it is more preferable that it is 20-100 mol%.

On the other hand, in the case where the hydrophobic resin contains a CH ₃ partial structure in the side chain portion, it is also preferred that the hydrophobic resin does not substantially contain a fluorine atom and a silicon atom. The content of the repeating unit having an atom or silicon atom is preferably 5 mol% or less, more preferably 3 mol% or less, more preferably 1 mol% or less, based on all repeating units in the hydrophobic resin. More preferably, it is ideally 0 mol%, ie it does not contain fluorine and silicon atoms. Moreover, it is preferable that hydrophobic resin is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom. More specifically, it is preferable that the repeating unit composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom is 95 mol% or more in the total repeating units of the hydrophobic resin. 97 mol% or more is more preferable, 99 mol% or more is further preferable, and ideally 100 mol%.

  The weight average molecular weight in terms of standard polystyrene of the hydrophobic resin is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000.

Moreover, the hydrophobic resin may be used alone or in combination.
The content of the hydrophobic resin in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass with respect to the total solid content in the composition of the present invention. 7 mass% is still more preferable.

  It is natural that the hydrophobic resin has few impurities such as metals, and the residual monomer or oligomer component is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, 0.05-1 mass% is still more preferable. Thereby, a composition having no change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is the range of 1-2.

  As the hydrophobic resin, various commercially available products can be used, and can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable.

  The reaction solvent, the polymerization initiator, the reaction conditions (temperature, concentration, etc.) and the purification method after the reaction are the same as described in the resin (A), but in the synthesis of the hydrophobic resin, the reaction concentration Is preferably 30 to 50% by mass.

[Surfactant]
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably further contains a surfactant, and a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant, silicon-based surfactant, It is more preferable to contain either one or two or more surfactants having both fluorine atoms and silicon atoms.

  When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains the above-mentioned surfactant, adhesion and development defects with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. It is possible to provide a resist pattern with less.

  Examples of the fluorine-based and / or silicon-based surfactant include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, JP 2002-277862 A, US Patent Nos. 5,405,720, 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511, 5,824,451 Surfactant can be mentioned, The following commercially available surfactant can also be used as it is.

  Examples of commercially available surfactants that can be used include EFTOP EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 and 4430 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176 and F189. , F113, F110, F177, F120, R08 (manufactured by Dainippon Ink & Chemicals, Inc.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (Manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (manufactured by Toa Gosei Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), F-top EF121, EF122A, EF122B, RF122C, EF125M , EF135M, EF351, 352, EF801, EF802, EF 01 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204D, 208G, 218G, 230G, 204D, 208D, 212D, 218, 222D (manufactured by Neos) Fluorine type surfactant or silicon type surfactant can be mentioned. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon surfactant.

  In addition to the known surfactants described above, the surfactant is derived from a fluoroaliphatic compound produced by a telomerization method (also called telomer method) or an oligomerization method (also called oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

  These surfactants may be used alone or in several combinations.

  The amount of the surfactant used is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent). is there.

[Carboxylic acid onium salt]
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may contain a carboxylic acid onium salt. Examples of the carboxylic acid onium salt include a carboxylic acid sulfonium salt, a carboxylic acid iodonium salt, and a carboxylic acid ammonium salt. In particular, as the carboxylic acid onium salt, an iodonium salt and a sulfonium salt are preferable. Furthermore, it is preferable that the carboxylate residue of the carboxylic acid onium salt of the present invention does not contain an aromatic group or a carbon-carbon double bond. As a particularly preferable anion moiety, a linear, branched, monocyclic or polycyclic alkylcarboxylic acid anion having 1 to 30 carbon atoms is preferable. More preferably, an anion of a carboxylic acid in which some or all of these alkyl groups are fluorine-substituted is preferable. The alkyl chain may contain an oxygen atom. This ensures transparency with respect to light of 220 nm or less, improves sensitivity and resolution, and improves density dependency and exposure margin.

  Fluoro-substituted carboxylic acid anions include fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, nonafluoropentanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorocyclohexanecarboxylic acid, 2 , 2-bistrifluoromethylpropionic acid anion and the like.

  These carboxylic acid onium salts can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent.

  The content of the carboxylic acid onium salt in the composition is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, more preferably, based on the total solid content of the composition of the present invention. 1 to 7% by mass.

[Other additives]
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention further has solubility in dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors and developers as necessary. A compound to be promoted (for example, a phenol compound having a molecular weight of 1000 or less, an alicyclic compound having a carboxyl group, or an aliphatic compound) and the like can be contained.

  Such a phenol compound having a molecular weight of 1000 or less is disclosed in, for example, JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, and the like. It can be easily synthesized by those skilled in the art with reference to the method described.

Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples thereof include, but are not limited to, dicarboxylic acids.
A pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter referred to as the pattern forming method of the present invention) will be described in detail below.

  Various materials used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and the pattern forming method of the present invention (for example, a resist solvent, a developer, a rinse solution, an antireflection film-forming composition, a top The coating forming composition or the like) preferably does not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 10 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially free (below the detection limit of the measuring device). Is most preferable.

  Examples of a method for removing impurities such as metals from the various materials include filtration using a filter. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. A filter that has been washed in advance with an organic solvent may be used. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination. Moreover, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.

  Moreover, as a method for reducing impurities such as metals contained in the various materials, a raw material having a low metal content is selected as a raw material constituting the various materials, and filter filtration is performed on the raw materials constituting the various materials. For example, the inside of the apparatus may be lined with Teflon (registered trademark), and distillation may be performed under a condition in which contamination is suppressed as much as possible. The preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.

  In addition to filter filtration, impurities may be removed with an adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

  The present invention also relates to an electronic device manufacturing method including the pattern forming method of the present invention described above, and an electronic device manufactured by this manufacturing method.

  The electronic device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA (Office Appliance) / media related equipment, optical equipment, communication equipment, etc.).

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the content of this invention is not limited by this.
<Synthesis of acid-decomposable resin>
Synthesis Example: Synthesis of Resin A-1 39 parts by mass of cyclohexanone was heated to 80 ° C. in a nitrogen stream. While stirring this solution, 8.89 parts by mass of a monomer represented by the following structural formula M-1, 9.11 parts by mass of a monomer represented by the following structural formula M-2, and represented by the following structural formula M-3 A mixed solution of 1.72 parts by mass of monomer, 73 parts by mass of cyclohexanone, and dimethyl 2,2′-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] over 6 hours. It was dripped. After completion of dropping, the mixture was further stirred at 80 ° C. for 2 hours. The reaction solution was allowed to cool, then reprecipitated and filtered with a large amount of methanol / water (mass ratio 9: 1), and the obtained solid was vacuum dried to obtain 18 parts by mass of the following resin A-1.

The weight average molecular weight (Mw: converted to polystyrene) obtained from GPC (carrier: Tetrahydrofuran; THF) of the obtained resin A-1 was Mw = 10500, and the dispersity was Mw / Mn = 1.62. . ^The composition ratio (molar ratio; corresponding in order from the left) measured by ¹³ C-NMR (Nuclear Magnetic Resonance) was 40/50/10.

  The same operations as in Synthesis Example 1 were performed to synthesize the following A-2 to A-14 and A-20 to A-22, which are acid-decomposable resins.

[Preparation of resist composition]
The components shown in the following Tables 2-1 to 2-4 are dissolved in the solvents shown in the same table, and a solution with a solid content concentration of 4% by mass is prepared for each, and further filtered through a polyethylene filter having a pore size of 0.05 μm. Thus, resist compositions (resist compositions of Examples and Comparative Examples) were prepared.

[Preparation of cross-linking solution]
As the crosslinking treatment liquid, the components shown in Table 2-2, Table 2-3 and Table 2-4 below were dissolved in the solvents shown in the same table to prepare a solution having a solid content concentration of 2% by mass.

  Abbreviations in Tables 2-1 to 2-4 are as follows.

(Acid-decomposable resin)
The structure of the resin used in the examples and comparative examples, the composition ratio (molar ratio) of the resin, the weight average molecular weight, and the degree of dispersion are shown below.

[Acid generator]
The structural formula of the acid generator (B) is shown below.

[Basic compounds]
The structural formula of the basic compound is shown below.

[Hydrophobic resin]
The structural formula of the hydrophobic resin, its composition ratio (molar ratio), weight average molecular weight and degree of dispersion are shown below. The composition ratio (molar ratio), weight average molecular weight, and degree of dispersion of each hydrophobic resin were determined by the same method as the acid-decomposable resin described above.

[Surfactant]
W-1: Megafuck F176 (manufactured by DIC Corporation) (fluorine-based)
W-2: Megafuck R08 (manufactured by DIC Corporation) (fluorine and silicon)
〔solvent〕
S1: Propylene Glycol Monomethyl Ether Acetate (PGMEA)
S2: Cyclohexanone S3: γ-Butyrolactone S4: Propylene Glycol Monomethyl Ether (PGME)
S5: Ethyl lactate [Crosslinking agent (D) used in the crosslinking treatment liquid]
The structural formula of the crosslinking agent (D) used in the crosslinking treatment liquid is shown below.

[Additives used with crosslinking agents]
Structural formulas of additives for improving the reaction rate of the crosslinking agent are shown below.

[Solvent used in the cross-linking solution]
The structural formula of the solvent used for the crosslinking treatment liquid is shown below.

Examples 1-22, Comparative Examples 1-2 [Organic solvent development → crosslinking treatment → alkali development]
On the silicon wafer, an organic antireflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied and baked at 205 ° C. for 60 seconds (organic antireflection film thickness 80 nm). The resist composition described in Table 3 below was applied thereon and baked at 90 ° C. for 60 seconds. Thereby, a resist film having a film thickness of 85 nm was formed.

  The obtained resist film was subjected to pattern exposure using an ArF excimer laser immersion scanner (SMTL XT1700i, NA 1.20, Dipole, outer sigma 0.900, inner sigma 0.800, Y deflection). . Ultra pure water was used as the immersion liquid.

  As the reticle, a 6% halftone mask having a pitch of 120 nm and line: space = 1: 1 was used.

  Then, after baking at 100 degreeC for 60 second (Post Exposure Bake: PEB), it cooled to room temperature.

  Next, it was developed by paddle with butyl acetate for 30 seconds, and then rinsed with a rinsing solution [Methyl Isobutyl Carbinol (MIBC)] for 30 seconds.

  Subsequently, this film was immersed in a crosslinking treatment solution described in Table 3 for 30 seconds, then taken out from the crosslinking treatment solution, and heated under the conditions described in the table to perform a crosslinking reaction. Thereafter, the substrate was rinsed with a rinsing solution [methyl isobutyl carbinol (MIBC)] for 10 seconds and then dried.

  Subsequently, the film was developed by padding with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 30 seconds and rinsed with pure water for 10 seconds.

  Thereafter, the wafer was rotated at a rotational speed of 4000 rpm for 30 seconds to obtain a line-and-space resist pattern having a pitch half the pitch on the mask.

<Evaluation>
[Limit resolution]
The line and space pattern obtained by the above pattern formation method was observed using a length-measuring scanning electron microscope (SEM (Scanning Electron Microscope), Hitachi, Ltd. S-9380II). The minimum half-pitch resolution was evaluated as the limit resolution.

  If the pattern separation was unclear and a line-and-space pattern having a pitch half the pitch on the mask could not be obtained, the evaluation was impossible and the column was left blank.

Examples 23 to 24 [first organic solvent development → crosslinking treatment → second organic solvent development]
The resist composition described in Table 4 below was used as the resist composition, the developer in the second development was changed from a TMAH aqueous solution to cyclohexanone, and water was changed to MIBC as the rinse liquid in the subsequent rinsing process. The same processing as in Examples 1 to 24 was performed to obtain a line and space resist pattern with a pitch of 60 nm.

<Evaluation>
[Limit resolution]
The limit resolution was evaluated by the same evaluation method as described above. The results are shown in Table 4.

  From the evaluation results shown in Table 3 and Table 4, it can be seen that the pattern formation method of the present invention suppresses bridging defects between patterns and provides a pattern with high limit resolution. In Comparative Examples 1 and 2, as a result of insolubilizing not only the pattern side wall (intermediate exposure amount region) but also the entire pattern by the crosslinking treatment, the upper part of the pattern remained, and the pattern separation was unclear.

10 ... substrate,
11: Low exposure area (unexposed area),
12: Region of intermediate exposure amount (intermediate exposure part),
13 ... High exposure area (exposure part)

Claims (9)

(I) forming an actinic ray-sensitive or radiation-sensitive film using an actinic ray-sensitive or radiation-sensitive resin composition containing the resin (A) containing an acid-decomposable group and a crosslinkable reactive group;
(Ii) irradiating the film with actinic rays or radiation;
(Iii) developing the film with a first developer containing an organic solvent, removing a low exposure area to form a negative pattern,
(Iv) reducing the solubility of the negative pattern in the intermediate exposure area in the second developer; and (v) developing the negative pattern using the second developer to obtain a high exposure area. The pattern formation method which includes the process of leaving only an intermediate | middle exposure amount area | region as a pattern by removing this in this order.   The pattern forming method according to claim 1, wherein the second developer is an alkali developer.   The pattern forming method according to claim 1, wherein the second developer contains an organic solvent.   The pattern forming method according to claim 1, wherein the step (iv) includes bringing a treatment agent that reacts with the crosslinkable reactive group into contact with the negative pattern.   The pattern formation method of any one of Claims 1-4 in which the said resin (A) contains the repeating unit which has an acid-decomposable group and a crosslinkable reactive group.   The pattern forming method according to claim 5, wherein in the repeating unit, the crosslinkable reactive group is included in a site that is eliminated by the action of an acid that is a partial structure of the acid decomposable group. The pattern forming method according to claim 6, wherein the acid-decomposable group is represented by the following general formula (1).
In general formula (1),
R ₁ and R ₂ each independently represent a substituent, L ₁ represents a (n + 1) -valent linking group, X represents a crosslinkable reactive group, n represents an integer of 1 or more, and * represents Represents the bonding position with the main chain of the resin (A). _Two selected from R ₁ , R ₂ and L ₁ may be linked to each other to form a ring. The pattern forming method according to claim 6, wherein the acid-decomposable group is represented by the following general formula (2).
In general formula (2),
R ₁ and R ₂ each independently represent a substituent, R ₃ and R ₄ each independently represent a hydrogen atom or a substituent, L ₂ represents an (n + 1) -valent linking group, and L ₃ Represents a single bond or a divalent linking group, X represents a crosslinkable reactive group, n represents an integer of 1 or more, and * represents a bonding position with the main chain of the resin (A). _Two selected from R ₁ , R ₂ and L ₂ may be connected to each other to form a ring, and R ₃ and R ₄ may be connected to each other to form a ring.   The manufacturing method of an electronic device containing the pattern formation method of any one of Claims 1-8.