JPWO2018003271A1 - Pattern forming method, method of manufacturing electronic device, actinic ray sensitive or radiation sensitive resin composition, and resist film - Google Patents

Abstract

Method for forming a pattern using an actinic ray-sensitive or radiation-sensitive resin composition film having excellent developability while having excellent water followability, a method for producing an electronic device, actinic ray-sensitive or radiation-sensitive resin Provided are a composition and a resist film. The pattern forming method comprises a resist film forming step of forming an actinic ray sensitive or radiation sensitive resin composition film on a substrate using an actinic ray sensitive or radiation sensitive resin composition, an exposure step, And a developing step, wherein the actinic ray-sensitive or radiation-sensitive resin composition has a resin A whose solubility in an alkali developer is increased by the action of an acid, and a compound B in which an acid is generated by irradiation with an actinic ray or radiation. And a combination of the resin C1 and the resin C2, and at least one of the resin C.

Description

  The present invention relates to a pattern forming method, a method of manufacturing an electronic device, an actinic ray-sensitive or radiation-sensitive resin composition, and a resist film.

With the miniaturization of the structures of various electronic devices such as semiconductor devices and liquid crystal devices, immersion exposure may be used to form finer resist patterns.
In the case of using an ArF excimer laser as a light source in immersion exposure, pure water is used as the immersion liquid in that the handling safety is high, the light transmittance at 193 nm is high, and the refractive index at 193 nm is high. Often

  In the case of forming a fine resist pattern, chemical amplification may be used as a method for forming a resist pattern. A method of forming a positive resist pattern using chemical amplification is described as an example. First, in the exposed area, the acid generator decomposes to form an acid. Subsequently, in the post-exposure bake (PEB: PostExposureBake), the alkali-insoluble group contained in the resin in the resist film is changed to an alkali-soluble group using the generated acid as a reaction catalyst, and the exposed portion is removed by alkali development. It is a method.

  When immersion exposure is applied to a resist film using chemical amplification, the resist film is in contact with the immersion liquid at the time of exposure, so that the resist film is denatured and / or constituents of the resist film from the resist film to the immersion liquid It is known that may exude.

  Further, in the case of immersion exposure, in the case of exposure using a scan type immersion exposure apparatus, it is also required that the immersion liquid also be moved at high speed following the high speed movement of the lens of the immersion exposure apparatus. As described above, it is known that in the case where the immersion liquid is water, the resist film is preferably hydrophobic. In Patent Document 1, a photoresist composition containing one or more resins, a photoactive component, and two or more substances substantially immiscible with one or more resins is applied on a substrate. A method of treating a photoresist composition comprising immersion exposing the photoresist layer to activating radiation for the photoresist composition, wherein the method is substantially immiscible A method is described wherein the substance comprises (i) a surface substance and (ii) an intermediate substance, wherein the surface substance and the intermediate substance have different surface energies.

JP, 2009-199058, A

  The present inventors applied the photoresist composition described in Patent Document 1 to the immersion exposure step and the development step, and the resist film formed of the photoresist composition has a water-following property (water tracking It has been found that although it has a certain level of properties, the developability during alkali development (hereinafter, also simply referred to as "developability") has not reached the level required nowadays. In the present specification, the water followability is a value that can be measured by the method described in the examples, and can the immersion liquid follow the high-speed movement of the exposure apparatus on the resist film during immersion exposure? Intended for the indicator.

Therefore, in the present invention, a pattern is formed using an actinic ray-sensitive or radiation-sensitive resin composition film (hereinafter, also referred to as "resist film") having excellent developability while having excellent water followability. The task is to provide a method. Another object of the present invention is to provide a method for producing an electronic device, an actinic ray-sensitive or radiation-sensitive resin composition, and a resist film.
In the present specification, the excellent developability refers to the developability of a resist film that can be measured by the method described in the examples described later, that is, pattern collapse, line edge roughness (LER), It is intended that each evaluation of scum and development defects has reached a practical level.

The inventors of the present invention have conducted intensive studies to achieve the above problems, and as a result, it is a pattern forming method including a resist film forming step, an exposure step, and a developing step described later. That the above-mentioned problems can be solved by containing the resin A, the compound B, the combination of the resin C1 and the resin C2, and at least one of the resins C, which are described later. The present invention has been completed.
That is, it discovered that the above-mentioned subject could be achieved by the following composition.

[1] A resist film forming step of forming an actinic ray sensitive or radiation sensitive resin composition film on a substrate using an actinic ray sensitive or radiation sensitive resin composition, an actinic ray sensitive or sensitive film Exposing the radiation-sensitive resin composition film to an actinic ray or radiation, developing the actinic ray-sensitive or radiation-sensitive resin composition film irradiated with the actinic ray or radiation using an alkaline developer, A pattern forming method comprising a developing step, wherein the actinic ray-sensitive or radiation-sensitive resin composition is resin A in which the solubility in an alkali developer is increased by the action of an acid, and irradiation with an actinic ray or radiation A pattern forming method comprising a compound B capable of generating an acid, a combination of a resin C1 and a resin C2, and at least one of a resin C.
The resin C1 contains at least one selected from the group consisting of the repeating unit represented by the formula X1, the group represented by the formula X2, and the group represented by the formula X3, and the resin C2 is And at least one selected from the group consisting of a group represented by the formula Y1, a group represented by the formula Y3, and a repeating unit represented by the formula Y2, and the resin C is a compound represented by the formula X1 And at least one selected from the group consisting of a group represented by Formula X2, and a group represented by Formula X3, and a group represented by Formula Y1 and represented by Formula Y3 And at least one selected from the group consisting of a group and a repeating unit represented by Formula Y2.
[2] When the actinic ray-sensitive or radiation-sensitive resin composition contains one or two or more specific resins selected from the group consisting of resin C1, resin C2 and resin C, all the specific ones The pattern formation method according to [1], wherein the resin contains a repeating unit derived from a monomer satisfying at least one formula selected from the group consisting of Formulas 3-5.
[3] The pattern formation method according to [2], wherein at least one of the specific resins contains a repeating unit derived from a monomer satisfying Formula 4 and Formula 6, or Formula 5 and Formula 6.
[4] [1], wherein R ₁ in the repeating unit represented by the formula X1 and R ₂ in the group represented by the formula X2 are alkyl groups substituted with three or more fluorine atoms The pattern formation method in any one of [3].
[5] Any one of [1] to [4], wherein R in the repeating unit represented by the formula Y2, and R in the group represented by the group represented by the formula Y1 and the group represented by the formula Y1 are hydrogen atoms A method for forming a pattern according to the above.
[6] R in the repeating unit represented by the formula Y2, and R in the group represented by the group represented by the formula Y1 and the group represented by the formula Y1 are each an alkyl group, aryl group or alkyl containing a substituent The pattern formation method in any one of [1]-[4] which is an amino group.
[7] An alkyl group or an aryl group in which R in the repeating unit represented by Formula Y2 and R in the group represented by Formula Y1 and the group represented by Formula Y3 are eliminated under basic conditions [6], the pattern formation method according to [6].
[8] The resin C and the resin C2 contain a repeating unit containing two or more at least one group selected from the group consisting of a group represented by the formula Y1 and a group represented by the formula Y3 [ The pattern formation method in any one of [1]-[7].
[9] [1] to [1], wherein the resin C, the resin C1, and the resin C2 are at least one polymer selected from the group consisting of (meth) acrylate derivatives, styrene derivatives, and allyl group-containing compounds The pattern formation method in any one of 8].
[10] The pattern forming method according to any one of [1] to [9], wherein at least one resin selected from the group consisting of resin C1, resin C2 and resin C contains an aromatic ring.
[11] The pattern forming method according to any one of [1] to [10], wherein the resin C1 and the resin C contain a repeating unit represented by Formula 7.
[12] Any one of [1] to [11], wherein the actinic ray-sensitive or radiation-sensitive resin composition contains a resin C and at least one selected from the group consisting of a resin C1 and a resin C2 The pattern formation method as described in.
[13] The pattern forming method according to any one of [1] to [12], wherein the resin A contains a repeating unit containing a lactone structure.
[14] The pattern formation method according to any one of [1] to [13], wherein the actinic ray-sensitive or radiation-sensitive resin composition further contains a solvent D.
[15] The pattern formation method according to any one of [1] to [14], wherein the film thickness of the actinic ray sensitive or radiation sensitive resin composition film is 80 nm or less.
[16] The pattern formation method according to any one of [1] to [15], wherein the exposure step is a liquid immersion exposure step.
[17] A method of manufacturing an electronic device, comprising the pattern forming method according to any one of [1] to [16].
[18] Resin A whose solubility in an alkali developing solution is increased by the action of an acid, Compound B which generates an acid when irradiated with an actinic ray or radiation, a combination of resin C1 and resin C2, and at least resin C An actinic ray-sensitive or radiation-sensitive resin composition containing one side and a side.
The resin C1 contains at least one selected from the group consisting of the repeating unit represented by the formula X1, the group represented by the formula X2, and the group represented by the formula X3, and the resin C2 is And at least one selected from the group consisting of a group represented by the formula Y1, a group represented by the formula Y3, and a repeating unit represented by the formula Y2, and the resin C is a compound represented by the formula X1 And at least one selected from the group consisting of a group represented by Formula X2, and a group represented by Formula X3, and a group represented by Formula Y1 and represented by Formula Y3 And at least one selected from the group consisting of a group and a repeating unit represented by Formula Y2.
[19] One or two or more specific resins selected from the group consisting of resin C1, resin C2 and resin C are contained, and all the specific resins are selected from the group consisting of formulas 3 to 5 The actinic-ray-sensitive or radiation-sensitive resin composition as described in [18], which contains a repeating unit derived from a monomer satisfying at least one of the formulas.
[20] The actinic ray-sensitive or radiation-sensitive compound according to [19], wherein at least one of the specific resins contains a repeating unit derived from a monomer satisfying Formula 4 and Formula 6, or Formula 5 and Formula 6, Resin composition.
[21] [18], wherein R ₁ in the repeating unit represented by the formula X1 and R ₂ in the group represented by the formula X2 are alkyl groups substituted with three or more fluorine atoms, The actinic ray-sensitive or radiation-sensitive resin composition as described in any one of [20].
[22] Any one of [18] to [21], wherein R in the repeating unit represented by the formula Y2, and R in the group represented by the group represented by the formula Y1 and the group represented by the formula Y1 are hydrogen atoms An actinic ray-sensitive or radiation-sensitive resin composition according to any one of the preceding items.
[23] R in the repeating unit represented by the formula Y2, and R in the group represented by the group represented by the formula Y1 and the group represented by the formula Y1 are each an alkyl group, aryl group or alkyl containing a substituent The actinic ray sensitive or radiation sensitive resin composition as described in any one of [18] to [21], which is an amino group.
[24] An alkyl group or an aryl group in which R in the repeating unit represented by Formula Y2 and R in the group represented by Formula Y1 and the group represented by Formula Y3 are eliminated under basic conditions The actinic ray-sensitive or radiation-sensitive resin composition according to [23], which is
[25] The resin C and the resin C2 contain a repeating unit containing two or more at least one group selected from the group consisting of a group represented by the formula Y1 and a group represented by the formula Y3 [ The actinic-ray-sensitive or radiation-sensitive resin composition as described in any one of 18] to [24].
[26] The resin C, the resin C1, and the resin C2 are at least one polymer selected from the group consisting of (meth) acrylate derivatives, styrene derivatives, and allyl group-containing compounds, [18] to [[18] 25. The actinic ray-sensitive or radiation-sensitive resin composition according to any of 25.
[27] The actinic ray sensitivity or sensitivity as described in any one of [18] to [26], wherein at least one resin selected from the group consisting of resin C1, resin C2 and resin C contains an aromatic ring Radiation-sensitive resin composition.
[28] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [18] to [27], wherein the resin C1 and the resin C contain a repeating unit represented by Formula 7.
[29] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [18] to [28], which contains a resin C, and at least one selected from the group consisting of a resin C1 and a resin C2. object.
[30] The actinic ray-sensitive or radiation-sensitive resin composition as described in any of [18] to [29], wherein the resin A contains a repeating unit containing a lactone structure.
[31] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [18] to [30], further containing a solvent D.
[32] A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [18] to [31].

  According to the present invention, it is possible to provide a pattern formation method using a resist film having excellent developability while having excellent water followability. Moreover, this invention can also provide the manufacturing method of an electronic device, actinic-ray-sensitive or radiation-sensitive resin composition, and a resist film.

Hereinafter, the present invention will be described in detail.
Although the description of the configuration requirements described below may be made based on the representative embodiments of the present invention, the present invention is not limited to such embodiments.
In addition, in this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.
In addition, the term "actinic ray" or "radiation" in the present specification means, for example, the emission line spectrum of a mercury lamp, and far ultraviolet radiation represented by an excimer laser, extreme ultraviolet (EUV) radiation, X-rays, and electron beams. Means etc. In the present specification, "light" means actinic rays and radiation. Unless otherwise specified, the "exposure" in the present specification means not only exposure by far ultraviolet rays represented by a mercury lamp and excimer laser, X-rays and EUV, etc., but also particle beams such as electron beams and ion beams. Also includes drawing.
Also, as used herein, "(meth) acrylate" represents acrylate and methacrylate. Moreover, in this specification, "(meth) acryl" represents an acryl and a methacryl. Also, as used herein, “(meth) acryloyl” represents acryloyl and methacryloyl. Also, as used herein, "(meth) acrylamide" refers to acrylamide and methacrylamide. Moreover, in this specification, "monomer" and "monomer" are synonymous. A monomer is distinguished from an oligomer and a polymer and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the “polymerizable compound” refers to a compound containing a polymerizable group, and may be a monomer or a polymer. The "polymerizable group" refers to a group involved in the polymerization reaction.

  In the following, first, the actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method according to the embodiment of the present invention will be described, and then the pattern forming method will be described step by step.

[Activated ray-sensitive or radiation-sensitive resin composition]
The actinic ray-sensitive or radiation-sensitive resin composition (hereinafter, also referred to as "resist composition") contains the following (1) to (3).
(1) Resin A in which the solubility in an alkali developer is increased by the action of an acid.
(2) Compound B which generates an acid upon irradiation with an actinic ray or radiation.
(3) A combination of the resin C1 and the resin C2, and at least one of the resin C.

Here, the resin C1 and the resin C2 contain the following (i) and (ii), respectively.
Resin C1:
(I) At least one selected from the group consisting of a repeating unit represented by Formula X1, a group represented by Formula X2, and a group represented by Formula X3.
Resin C2:
(Ii) At least one selected from the group consisting of a group represented by the formula Y1, a group represented by the formula Y3, and a repeating unit represented by the formula Y2.
On the other hand, the resin C contains both the above (i) and (ii).

The resist composition is used for positive development (development in which an unexposed area remains as a pattern and an exposed area is removed). That is, development is performed using an alkaline developer.
When immersion exposure is applied to a resist film using chemical amplification, it is known that the resist film is preferably hydrophobic. When the immersion liquid is water, it is considered that the water easily follows the high-speed movement (scan movement) of the exposure apparatus.
According to the study of the present inventors, it has been found that a general highly hydrophobic resist film has a problem in developability during alkali development. The present inventors believe that this is because the alkali developer does not penetrate sufficiently into the resist film because the resist film is hydrophobic.

The resist composition contains at least one of the combination of the resin C1 and the resin C2 and the resin C. A combination of resin C1 and resin C2 and resin C is
(I) at least one selected from the group consisting of a repeating unit represented by the formula X1, a group represented by the formula X2, and a group represented by the formula X3, and
(Ii) at least one selected from the group consisting of a group represented by the formula Y1, a group represented by the formula Y3, and a repeating unit represented by the formula Y2;
Here, since (i) contains a fluorine atom or a silicon atom in the structure thereof, these are unevenly distributed on the resist film surface, the surface hydrophobicity tends to be high, and contributes to the improvement of the water followability.
On the other hand, (ii) contains a hydrophilic group in its structure. The hydrophilic group has the function of facilitating dissolution of the resist film in an alkaline developer, and contributes to the improvement of the developability.
The resist composition contains the resin containing (i) and (ii), or a combination of a resin containing (i) and a resin containing (ii), whereby the (i) and the resin containing the (i) and (ii) are combined. It is presumed that the synergistic effect of (ii) is obtained, and the effect of the present invention is obtained.
The above is speculation, and the scope of the present invention is not limited to the scope in which the effect can be obtained by the above mechanism of action.

  Hereinafter, the aspect is demonstrated for every component which the said resist composition contains.

[Resin A in which the solubility in an alkali developer is increased by the action of an acid]
Resin A is a resin whose solubility in an alkali developing solution is increased by the action of an acid, and is decomposed by the action of acid into the main chain or side chain of the resin, or both the main chain and side chain, It is a resin having a generated group (hereinafter also referred to as "acid-degradable group").

  Examples of the alkali-soluble group include phenolic hydroxyl group, carboxyl group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide Group, bis (alkyl carbonyl) methylene group, bis (alkyl carbonyl) imide group, bis (alkyl sulfonyl) methylene group, bis (alkyl sulfonyl) imide group, tris (alkyl carbonyl) methylene group, and tris (alkyl sulfonyl) methylene And the like.

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

Each of R _{01 and} R ₀₂ independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
The acid-degradable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like.

The resin A preferably has a repeating unit having an acid decomposable group. As a repeating unit which has an acid decomposable group, the repeating unit represented by following formula (AI) is preferable.

In formula (AI),
Xa ₁ represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. T represents a single bond or a divalent linking group.
Each of Rx _{1 to} Rx ₃ independently represents an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic).
At least two of Rx _{1 to} Rx ₃ may be combined to form a cycloalkyl group (monocyclic or polycyclic).

Formula (A1) will be described in more detail.
Examples of the divalent linking group of T include an alkylene group, -COO-Rt- group, and -O-Rt- group. In formula, Rt represents an alkylene group or a cycloalkylene group.

Rx ₁ is a methyl group or an ethyl group, aspects by bonding and Rx ₂ and Rx ₃ form a cycloalkyl radical as defined above, and / or _at least one of the above-mentioned cycloalkyl Rx 1 to Rx ₃ The aspect which is group is preferable.
_{-C (Rx 1) (Rx 2} ) (Rx 3) group is an acid-decomposable group in the formula (AI), at least one of the substituents - have a _(L) the group represented by n1 -P May be Here, L represents a divalent linking group, n ₁ represents 0 or 1, and P represents a polar group.

  Examples of the divalent linking group for L include a linear or branched alkylene group, a cycloalkylene group and the like, and the number of atoms of the divalent linking group as L is preferably 20 or less, and 15 or less. More preferable. The above linear or branched alkylene group and cycloalkylene group preferably have 8 or less carbon atoms. The linear or branched alkylene group or cycloalkylene group may have a substituent, and examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, and an alkoxy group 1-4), a carboxyl group, the alkoxy carbonyl group (C2-C6) etc. are mentioned.

  Examples of the polar group of P include groups containing a hetero atom such as a hydroxyl group, a ketone group, a cyano group, an amido group, an alkylamide group, a sulfonamide group, a lower ester group and a lower sulfonate group. Here, "lower" is preferably a group having 2 to 3 carbon atoms. The preferred polar group is a hydroxyl group, a cyano group or an amido group, more preferably a hydroxyl group.

The group represented by-(L) _n1 -P is a linear or branched alkyl group (for example, having a hydroxyl group, a cyano group, an amido group, an alkylamido group, or a sulfonamide group) as n1 = 1 Preferably, it has 1 to 10 carbon atoms and a cycloalkyl group (preferably 3 to 15 carbon atoms), preferably an alkyl group having a hydroxyl group (preferably 1 to 5 carbon atoms, and more preferably 1 carbon atom). And 3).

Among them, it is preferable that P is a hydroxyl group, n1 is 0 or 1, and L is a linear or branched alkylene group (preferably having a carbon number of 1 to 5).
The group represented by -C (Rx ₁ ) (Rx ₂ ) (Rx ₃ ) in formula (AI) preferably has 1 to 3 groups represented by-(L) _n1 -P, 1 or It is more preferable to have two, and it is most preferable to have one.
The repeating unit represented by the formula (AI) is preferably a repeating unit represented by the following formula (1-1).

In formula (1-1),
R ₃ is the same as Xa _{1 in} formula (AI).
R ₄ and R ₅ are the same as Rx ₁ and Rx _{2 in} Formula 1.
- _(L) group represented by n1 -P has the formula (A1) for - the same as the group represented by _(L) n1 -P.
p represents an integer of 1 to 3; p is preferably 1 or 2, more preferably 1.

  The monomer corresponding to the repeating unit of Formula (A1) can be synthesize | combined by the method of Unexamined-Japanese-Patent No. 2006-16379, for example.

  20-50 mol% is preferable with respect to all the repeating units in resin (A), and, as for the content rate of the repeating unit which has an acid-degradable group, 25-45 mol% is more preferable.

  Preferred embodiments of the acid-degradable group include the repeating units described in paragraphs 0049 to 0054 of JP-A-2010-44358 (hereinafter referred to as "Document A"), and the contents described above are referred to herein. Be incorporated.

  Resin A preferably further has a repeating unit having at least one group selected from the group consisting of a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group, and a repeating unit having a lactone group (lactone structure) It is more preferable to contain

The repeating unit having a lactone structure that may be contained in the resin A will be described.
As the lactone structure, any may be used, preferably a 5- to 7-membered ring lactone structure, and a bicyclo structure or a spiro structure is formed in the 5- to 7-membered ring lactone structure to form a condensed ring of another ring structure Is more preferable. It is more preferable to have a repeating unit having a lactone structure represented by any of the following formulas (LC1-1) to (LC1-17). Also, the lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), (LC1-17), and specific The line edge roughness and the development defect are improved by using the lactone structure of

The lactone structure moiety may or may not have a substituent (Rb ₂ ). As a preferable substituent (Rb ₂ ), an alkyl group having 1 to 8 carbon atoms (in the alkyl group, a hydrogen atom may be substituted with a fluorine atom), a cycloalkyl group having 4 to 7 carbon atoms, and a carbon number The alkoxy group of 1-8, a C1-C8 alkoxycarbonyl group, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, an acid-degradable group etc. are mentioned. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-degradable group. n2 represents an integer of 0 to 4; When n2 is 2 or more, plural substituents (Rb ₂ ) may be the same or different, and plural substituents (Rb ₂ ) may be combined to form a ring.

As a repeating unit which has a lactone structure represented by either of Formula (LC1-1)-(LC1-17), the repeating unit represented by a following formula (AII) can be mentioned.

In formula (AII),
Ab ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms which may have a substituent. Preferred examples of the substituent which the alkyl group of Ab ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom of Ab ₀ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Ab ₀ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and a hydrogen atom or a methyl group is particularly preferable.

  A represents a -COO- group or a -CONH- group.

Ab is a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether bond, an ester bond, an ester bond, a carbonyl group, an amide bond, a urethane bond or a urea bond, or a combination thereof And a divalent linking group. Preferably, it is a single bond and a divalent linking group represented by -Ab ₁ -CO _2- .

Ab ₁ is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.
n represents an integer of 1 to 5; n is preferably 1 or 2, and more preferably 1.

  V represents a group having a structure represented by any one of formulas (LC1-1) to (LC1-17).

  Specific examples of the repeating unit containing a lactone structure include, for example, the repeating units described in paragraphs 0064 to 0067 of Document A, and the above contents are incorporated herein.

The resin A preferably contains a repeating unit containing a lactone structure represented by the following formula (3).

In formula (3),
A represents an ester bond (-COO-) or an amide bond (-CONH-).
When there are a plurality of R _{0 s} , each independently represents an alkylene group, a cycloalkylene group, or a combination thereof.

  Z's each independently represent an ether bond, an ester bond, a carbonyl group, an amide bond, a urethane bond or a urea bond, when there are a plurality of Z's.

R ₈ represents a monovalent organic group having a lactone structure.

n represents the number of repetitions of the structure represented by _-R 0 -Z- within the repeating unit represented by formula (3) represents an integer of 1 to 5. n is preferably 1 or 2, and more preferably 1.

R ₇ represents a hydrogen atom, a halogen atom or an alkyl group which may have a substituent.

The alkylene group and cycloalkylene group of R ₀ may have a substituent.
Z is preferably an ether bond or an ester bond, particularly preferably an ester bond.

  As a repeating unit containing the lactone structure represented by the said Formula (3), the repeating unit as described in Paragraph 0079 of a document A is mentioned, The said content is integrated in this specification.

As a repeating unit which has a lactone structure, the repeating unit represented by following formula (3-1) is more preferable.

In formula (3-1),
R ₇ , A, R ₀ , Z and n are as defined in the above formula (3).
R ₉ independently represents an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an alkoxy group when there are two or more, and when there are two or more, two R ₉ are bonded to each other to form a ring May be formed.

X represents an alkylene group, an oxygen atom or a sulfur atom.
m is the number of substituents and represents an integer of 0 to 5; m is preferably 0 or 1. When m = 1, R ₉ is preferably substituted at the α-position or β-position of the carbonyl group of lactone, particularly preferably at the α-position.
The alkyl group of R _9, preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, most preferably a methyl group. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups. Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group and the like. Examples of the substituent include an alkoxy group such as a hydroxyl group, a methoxy group and an ethoxy group, and a halogen atom such as a cyano group and a fluorine atom. R ₉ is more preferably a methyl group, a cyano group or an alkoxycarbonyl group, and still more preferably a cyano group.
Examples of the alkylene group of X include a methylene group and an ethylene group. X is preferably an oxygen atom or a methylene group, and more preferably a methylene group.

  Specific examples of the repeating unit containing a lactone structure represented by the formula (3-1) include the repeating units described in paragraphs 0083 to 0084 of Document A, and the above contents are incorporated in the present specification.

  The repeating unit having a lactone group usually has an optical isomer, but any optical isomer may be used. In addition, one optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one type 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 is preferably 15 to 60 mol%, more preferably 20 to 50 mol%, and still more preferably 30 to 50 mol%, based on all repeating units in the resin.

The resin A preferably has a repeating unit having a hydroxyl group or a cyano group which is not included in the formulas (AI) and (AII). Thereby, the substrate adhesion and the developer affinity are improved. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted by a hydroxyl group or a cyano group. As an alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted by the hydroxyl group or the cyano group, an adamantyl group, a diamantyl group, and a norbornane group are preferable. As a preferable alicyclic hydrocarbon structure substituted by the hydroxyl group or the cyano group, the partial structure represented by following formula (VIIa)-(VIId) is preferable.

In formulas (VIIa) to (VIIc),
Each of R ₂ c to R ₄ c 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 remainder is a hydrogen atom. In formula (VIIa), more preferably, _two of R ₂ c to R ₄ c are a hydroxyl group and the remainder is a hydrogen atom.

  As repeating units having a partial structure represented by formulas (VIIa) to (VIId), the repeating units described in paragraphs 0090 to 0091 of Document A can be mentioned, and the above contents are incorporated in the present specification.

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

  As a repeating unit which has a hydroxyl group or a cyano group, the repeating unit as described in Paragraph 0093 of document A is mentioned, The said content is integrated in this specification.

  The resin A preferably has a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bisulsulfonylimide group, and an aliphatic alcohol (for example, hexafluoroisopropanol group) in which the α position is substituted with an electron withdrawing group. It is more preferable to have a repeating unit. By including a repeating unit having an alkali-soluble group, the resolution in contact hole applications is increased. As a repeating unit having an alkali-soluble group, a repeating unit in which an alkali-soluble group is directly bonded to the main chain of a resin such as a repeating unit of acrylic acid and methacrylic acid, or an alkali in the resin main chain via a linking group A repeating unit to which a soluble group is bonded, and further, a repeating unit in which an alkali soluble group is introduced at the end of a polymer chain by using a polymerization initiator having an alkali soluble group and / or a chain transfer agent at the time of polymerization is preferable. The linking group may have a monocyclic or polycyclic hydrocarbon structure. Particularly preferred are repeating units of acrylic acid and methacrylic acid.

The resin A preferably further contains a repeating unit represented by the formula (I) which has neither a hydroxyl group nor a cyano group.

In formula (I), 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. As Ra, for example, a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group can be mentioned. * Represents a bonding position.

In the resin A, the molar ratio of each repeating structural unit is the dry etching resistance of the resist and / or the standard developing solution suitability, the substrate adhesion, the resist profile, and further, the general performance of the resist such as resolution, heat resistance, sensitivity, etc. Are set appropriately to adjust the
When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is for ArF exposure, from the viewpoint of transparency to ArF light, it is preferable that the resin A does not have an aromatic group.

  Moreover, it is preferable that resin A does not contain a fluorine atom and a silicon atom.

  Resin A can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a batch polymerization method in which monomer species and an initiator are dissolved in a solvent and polymerization is carried out by heating, a solution of monomer species and an initiator is added dropwise over 1 to 10 hours to a heating solvent. The dropping polymerization method etc. are mentioned, and the drop polymerization method is preferable. As the reaction solvent, for example, ethers such as tetrahydrofuran, 1,4-dioxane, 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, a propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, polymerization is performed using the same solvent as the solvent used for the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. This makes it possible to suppress the generation of particles during storage.

  The weight average molecular weight of the resin A is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, and still more preferably 3, as a polystyrene conversion value by GPC (Gel Permeation Chromatography) method. 000 to 15,000, particularly preferably 5,000 to 13,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and / or dry etching resistance can be prevented, and developability is deteriorated or viscosity is increased to form a film. It is possible to prevent deterioration.

In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the compounding ratio of the resin A in the entire composition is preferably 50 to 99% by mass, more preferably 70 to 98% by mass in the total solid content. .
In the present invention, the resin A may be used alone or in combination of two or more.

[Compound B that generates an acid upon irradiation with actinic rays or radiation]
The actinic ray-sensitive or radiation-sensitive resin composition contains a compound capable of generating an acid upon irradiation with an actinic ray or radiation (hereinafter, also referred to as an "acid generator").

  As an acid generator, a photo-cationic polymerization photoinitiator, a photo-radical polymerization photoinitiator, a dye decoloring agent, a photo-discoloring agent, or an irradiation with an actinic ray or radiation used in a micro resist or the like Known compounds capable of generating an acid and mixtures thereof can be appropriately selected and used.

  For example, diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imidosulfonates, oxime sulfonates, diazodisulfones, disulfones, o-nitrobenzyl sulfonates can be mentioned.

Furthermore, compounds capable of generating an acid by the action of light described in U.S. Pat. No. 3,779,778 and European Patent No. 126,712 can also be used.
Among preferred acid generators, compounds represented by the following formulas (ZI), (ZII) and (ZIII) can be mentioned.

In the above formula (ZI),
Each of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ independently represents an organic group.
The carbon number of the organic group as R _{201, R 202} and _{R 203} is generally from 1 to 30, preferably 1 to 20.
It is also possible to form the two members ring structure of R ₂₀₁ to R _203, 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).
Z < ^- > represents a non-nucleophilic anion.

Examples of the non-nucleophilic anion as Z 2 ^- include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, a tris (alkylsulfonyl) methyl anion and the like.

  The "non-nucleophilic anion" is an anion which has a significantly low ability to cause a nucleophilic reaction, and is an anion which can suppress the time-lapse decomposition by an intramolecular nucleophilic reaction. This improves the temporal stability of the resist.

As more preferable (ZI) components, compounds (ZI-1), (ZI-2) and (ZI-3) described below can be mentioned.
The compound (ZI-1) is at least one of the aryl groups _R 201 _{to R 203} in formula (ZI), arylsulfonium compounds, namely, compounds containing an arylsulfonium as a cation.

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

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

In 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 represent a hydrogen atom, an alkyl group or a cycloalkyl group.

Each of R _x and R _y independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.

Any two or more of R _1c to R _{5c, R 6c} and _{R 7c,} and _{R x} and _{R y} may combine with each other to form a ring structure, the ring structure may contain an oxygen atom, a sulfur atom And may contain an ester bond or an amide bond. Any two or more of R _1c to R _{5c, R 6c} and _{R 7c,} and as the group _{R x} and _{R y} are formed by combined include a butylene group and a pentylene group.
Zc ^- represents a non-nucleophilic anion, in formula (ZI) Z ^- and include the same non-nucleophilic anion.

In formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.
The aryl group of R _{204 to} R ₂₀₇ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. Aryl group R ₂₀₄ to R ₂₀₇ represents an oxygen atom, a nitrogen atom, may be an aryl group containing a heterocyclic structure containing a sulfur atom. As an aryl group containing a heterocyclic structure, for example, pyrrole residue (a group formed by loss of one hydrogen atom from pyrrole), or furan residue (formed by loss of one hydrogen atom from furan) Groups, thiophene residues (groups formed by loss of one hydrogen atom from thiophene), indole residues (groups formed by loss of one hydrogen atom from indole), benzofuran residues (Group formed by loss of one hydrogen atom from benzofuran), benzothiophene residue (group formed by loss of one hydrogen atom from benzothiophene), and the like can be mentioned.

Z ^- represents a non-nucleophilic anion, in Z the formula (ZI) ^- may be the same as the non-nucleophilic anion.
As an acid generator, the compound represented by following formula (ZIV), (ZV), (ZVI) can be mentioned further.

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

Among the acid generators, more preferred are the compounds represented by formulas (ZI) to (ZIII).
Further, as the acid generator, a compound capable of generating an acid containing one sulfonic acid group or one imido group is preferable, and more preferably a compound capable of generating perfluoroalkanesulfonic acid, substituted with a fluorine atom or a group containing a fluorine atom Compounds that generate the above aromatic sulfonic acid or compounds that generate an imide acid substituted with a fluorine atom or a group containing a fluorine atom, and more preferably a fluorine-substituted alkanesulfonic acid or a fluorine-substituted benzenesulfonic acid A fluoronium substituted imidic acid or a sulfonium salt of a fluorine substituted methide acid. The acid generator which can be used is particularly preferably a fluorine-substituted alkanesulfonic acid, a fluorine-substituted benzenesulfonic acid or a fluorine-substituted imidic acid in which the pKa of the generated acid is pKa = -1 or less, and the sensitivity is improved.
Among the acid generators, particularly preferred examples are listed below.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator in the actinic ray-sensitive or radiation-sensitive resin composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total solid content of the composition. %, More preferably 1 to 7% by mass.

[Resin C1, Resin C2, and Resin C]
The actinic ray-sensitive or radiation-sensitive resin composition contains at least one of the combination of the resin C1 and the resin C2 and the resin C.

<Resin C1>
The resin C1 is a resin containing the following (i).
(I) At least one selected from the group consisting of a repeating unit represented by Formula X1, a group represented by Formula X2, and a group represented by Formula X3.
The resin C1 preferably contains the following (ib).
(Ib) at least one selected from the group consisting of a repeating unit represented by Formula X1, a repeating unit containing a group represented by Formula X2, and a repeating unit containing a group represented by Formula X3 Repeating unit X.

In the repeating unit represented by the formula X1, in the group represented by the formula X2, and in the group represented by the formula X3, L represents a single bond or a linking group. The linking group is not particularly limited, and in Formula X1 it may be a (n1 + 1) linking group, in Formula X2 it may be a divalent linking group, and in Formula X3 it may be (n3 + 1) As long as it is a linking group of Each of n1 and n3 independently represents an integer of 1 or more.
The divalent linking group is not particularly limited, and specific examples thereof include an alkylene group, and a divalent aliphatic hydrocarbon group such as a cycloalkylene group, an arylene group such as a phenylene group, an ether group, and a thioether group. One group selected from the group consisting of a carbonyl group, an ester group, an amido group, a urethane group, and a urea group, or a combination thereof, and the like can be mentioned.
The (n1 + 1) -valent linking group (same as above when n1 + 1 is 2) and the (n3 + 1) -valent linking group (same as above when n3 + 1 is 2) are not particularly limited. For example, a group represented by any one of the following formulas (A) to (D), a group obtained by combining them, and the like can be mentioned.

In the above formulas (A) to (D),
L ⁴ represents a trivalent group. T ³ represents a single bond or a divalent linking group, and three T ^{3 s} may be the same as or different from each other.
L ⁵ represents a tetravalent group. T ⁴ represents a single bond or a divalent linking group, and four T ^{4 s} may be the same as or different from each other.
L ⁶ represents a pentavalent group. T ⁵ represents a single bond or a divalent linking group, five T ⁵ may be different even identical to each other exist.
L ⁷ represents a hexavalent group. T ⁶ represents a single bond or a divalent linking group, and six T ^{6 s} may be the same as or different from each other.
^{Incidentally, T 3, T 4, T} 5 and the definition of the divalent linking group represented by T ⁶ are the same as those defined divalent linking group represented by the above-mentioned L.

The (n1 + 1) -valent linking group and the (n3 + 1) -valent linking group may be groups represented by the following formulas (K) to (O), or a combination thereof. In the formulae, * represents a bonding position.

In the repeating units represented by the formula X1, R ₁ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom.
Further, in the group represented by the formula X2, R ₂ represents a fluorine atom, an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, or -Si (R ₁₀ ) ₃ .
It does not specifically limit as a fluorine atom substituted alkyl group, For example, the group by which the hydrogen atom of the C1-C30 alkyl group was substituted by the fluorine atom is mentioned. Among them, an alkyl group substituted with 3 or more fluorine atoms is preferable. R ₁₀ represents an alkyl group, and the carbon number of R ₁₀ is not particularly limited, and is preferably 1 to 8, and more preferably 1 to 4.
Further, in the group represented by the formula X3, R ₁₀ represents an alkyl group, and the aspect is as described above.

  Ar represents an aromatic hydrocarbon ring group. The aromatic hydrocarbon ring group preferably has 6 to 10 carbon atoms, and may be monocyclic or polycyclic, and may contain a substituent. The aromatic hydrocarbon ring group is not particularly limited, and examples thereof include a benzene ring group and a naphthalene ring group.

  n1, n2 and n3 represent an integer of 1 or more. The upper limit value of n1, n2 and n3 is not particularly limited, and in general, 3 or less is preferable. In the above formulae, * represents a bonding position.

In the repeating unit represented by the formula X1, R _A represents a hydrogen atom or a monovalent substituent. The monovalent substituent is not particularly limited, and examples thereof include a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a halogenated alkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, and the like. Nitro group, carboxyl group, aryloxy group, silyloxy group, heterocyclic oxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryl An oxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or aryl Phonyl, acyl, aryloxycarbonyl, alkoxycarbonyl, carbamoyl, aryl or heterocyclic azo, imide, phosphino, phosphinyl, phosphinyloxy, phosphinylamino, silyl, adamantyl And groups in which two or more of these are combined, and the like.
As _RA , a hydrogen atom or a halogenated alkyl group is preferable, and a hydrogen atom or an alkyl group in which at least one hydrogen atom of the alkyl group is substituted with a fluorine atom is more preferable, and a hydrogen atom or a trifluoro Methyl is more preferred.

  Specific examples of the repeating unit represented by formula X1 are shown below. However, the said repeating unit is not limited to the following specific examples.

Specific examples of the group represented by formula X2 are shown below. However, the above groups are not limited to the following specific examples. In the following formulae, "Me" represents a methyl group, and * represents a bonding position.

The specific example of group represented by Formula X3 is shown. However, the above groups are not limited to the following specific examples. In the following formulas, * represents a bonding position.

As resin C1, it is preferable to contain the said repeating unit X.
The repeating unit containing a group represented by Formula X2 is preferably a repeating unit based on a monomer containing a group represented by Formula X2, and the monomer more preferably contains a polymerizable group.
Further, the repeating unit containing a group represented by the formula X3 is preferably a repeating unit based on a monomer containing a group represented by the formula X3, and the above-mentioned monomer preferably contains a polymerizable group. preferable.
It does not specifically limit as a polymeric group which the said monomer contains, It is preferable that it is group which has ethylenic unsaturated bonds, such as a (meth) acryloyl group and a vinyl group.

Specific examples of the repeating unit containing a group represented by the formula X2 include the following repeating units. In addition, the said repeating unit is not limited to the following specific example.

Specific examples of the repeating unit containing a group represented by Formula X3 include the following repeating units. In addition, the said repeating unit is not limited to the following specific example.

The resin C1 and the resin C described later preferably contain a repeating unit represented by the following formula 7.

In the formula, R represents at least one selected from the group consisting of a trialkylsilyl group, a fluorinated alkyl group having 2 or more carbon atoms, and a tertiary alkyl group, and R _A represents a hydrogen atom or a monovalent atom And n represents an integer of 2 or more.
Incidentally, in the repeating unit represented by formula 7, R _A is the same as the groups described as R _A in the formula X1.

The content of the repeating unit X in the resin C1 is not particularly limited, but is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, based on all repeating units in the resin C1.
The resin C1 may contain one or two or more repeating units X. When resin C1 contains 2 or more types of repeating units X, it is preferable that total content is in the said range.
When the content of the repeating unit X in the resin C1 is 50 mol% or more, the resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition has more excellent developability.

(Repeating unit Z)
The resin C1 may contain a repeating unit Z other than the repeating unit X and the repeating unit Y described later. As the repeating unit Z, for example, a repeating unit containing a group represented by the following formula K1 or a group represented by K2 can be mentioned. In the following formulas, * represents a bonding position.

In the group represented by the formula K1 and the group represented by the formula K2, L represents a single bond or a linking group, and the aspect of L in the formula K1 is the same as L in the formula X1, and the formula The aspect of L in K2 is the same as L in formula X2. Ar represents an aromatic hydrocarbon ring group, and the aspect of the aromatic hydrocarbon ring group is the same as Ar in formula X2. R _X represents a linear, cyclic or branched alkyl group in which neither a fluorine atom nor a silicon atom is substituted, and a plurality of R _X may be the same or different. It does not restrict | limit especially as carbon number of the said alkyl group, 4 or more are preferable.
n4 and n5 each represent an integer of 1 or more, and a plurality of R _{X s} may be bonded to each other to form a ring.

Specific examples of the repeating unit Z are shown below. However, repeating unit Z which resin C1 may contain is not limited to the following.

Further, the repeating unit Z may have the following structure.

It does not specifically limit as content of the repeating unit Z in resin C1, 0-70 mol% is preferable with respect to all the repeating units in resin C1, and 5-50 mol% is more preferable.
The resin C1 may contain one or two or more repeating units Z. When resin C1 contains 2 or more types of repeating units Z, it is preferable that total content is in the said range.

The weight average molecular weight of the resin C1 is not particularly limited, and is preferably 6000 to 50000, more preferably 7000 to 50000, still more preferably 7500 to 40000 as a polystyrene conversion value measured by GPC (Gel Permeation Chromatography) method. -30000 is particularly preferred.
The resist film formed using the said actinic-ray-sensitive or radiation-sensitive resin composition as the weight average molecular weight of resin C1 is 7000 or more has more excellent water followability.
For GPC measurement, for example, apparatus: "Alliance GPC 2000 (manufactured by Waters)", column: TSKgel GMH ₆ -HT x 2 + TSKgel GMH _6- HTL x 2 (both 7.5 mm ID x 30 cm, manufactured by Tosoh Corporation), Column temperature: 140 ° C. Detector: Differential refractometer, mobile phase: can be performed under the configuration and conditions of a solvent (eg o-dichlorobenzene etc.), the configuration of molecular weight is determined using polystyrene standard to determine average molecular weight be able to.

The content of the resin C1 in the actinic ray-sensitive or radiation-sensitive resin composition is not particularly limited, and relative to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition, 0.1%. -6 mass% is preferable, and 0.2-3 mass% is more preferable.
The resin C1 may be used alone or in combination of two or more. When using 2 or more types of resin C1 together, it is preferable that the total content of resin C1 in the said actinic-ray-sensitive or radiation-sensitive resin composition is in the said range.

<Resin C2>
The resin C2 is a resin containing the following (ii).
(Ii) At least one selected from the group consisting of a group represented by the formula Y1, a group represented by the formula Y3, and a repeating unit represented by the formula Y2.
It is preferable to contain the following (iib) as resin C2.
(Iib) at least one selected from the group consisting of a repeating unit containing a group represented by formula Y1, a repeating unit containing a group represented by formula Y3, and a repeating unit represented by formula Y2 Repeating unit Y.
As resin C2, it is more preferable to contain the following (iic).
(Iic) at least one repeating unit selected from the group consisting of a repeating unit containing two or more groups represented by the group represented by the formula Y1 or a group represented by Y3, and a repeating unit represented by the formula Y2.
As resin C2, it is still more preferable to contain the following (iid).
(Iid) A repeating unit containing two or more at least one group selected from the group consisting of a group represented by the formula Y1 and a group represented by the formula Y3.

In Formula Y1 and Formula Y3, L represents a single bond or a linking group. The aspect of L is the same as L in the above formula X2. R ₃ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom. The aspect of R ₃ is the same as R ₁ in the above formula X1 and R ₂ in the above formula X2.
In formula Y2, R _A represents a hydrogen atom or a monovalent substituent. The definition of the monovalent substituent is the same as the definition of the monovalent substituent represented by _RA in Formula X1 described above.
In formulas Y1 to Y3, R represents a hydrogen atom or a monovalent substituent. The definition of the monovalent substituent is the same as the definition of the monovalent substituent represented by _RA in Formula X1 described above.
R is preferably a hydrogen atom.
R is preferably an alkyl group containing a substituent, an aryl group or an alkylamino group.
The alkyl group in the substituent-containing alkyl group may be linear, branched or cyclic. Further, the number of carbon atoms contained in the above alkyl group is not particularly limited, and is preferably 1 to 20. Further, the type of substituent in the alkyl group containing a substituent is not particularly limited, and examples thereof include a halogen atom (preferably, a fluorine atom). Among them, as the alkyl group containing a substituent, an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom is preferable.

In addition, R is preferably an alkyl group or an aryl group which dissociates under basic conditions. By "an alkyl group or an aryl group that dissociates under basic conditions" is intended a group that dissociates under basic conditions to yield a hydrophilic group.
Preferred examples of the alkyl group or aryl group which dissociates under basic conditions include one or more hydrogen atoms at any position, an electron group such as a halogen atom such as a fluorine atom, a nitro group, and a cyano group. Included are groups substituted with attractive groups.

L _A represents a single bond when R is a hydrogen atom.
L _A represents a linking group when R is a monovalent substituent. The aspect of the linking group is the same as L in the above formula X2.
In the case of R is a monovalent substituent, as the L _A, may be a divalent linking group represented by the following formula (L _Y2).

In the formula (L _Y2 ), L _B and L _C each independently represent a single bond or a divalent linking group, and V is represented by the above formulas (LC1-1) to (LC1-17) The bivalent group which remove | eliminated two hydrogen atoms of arbitrary positions from the group containing this structure is represented.
When L _B and L _C are divalent linking groups, the aspect is the same as L as the divalent linking group in the formula X2. Here, * represents a bonding position.
Specific examples of the divalent linking group represented by the above formula (L _Y2 ) are shown below. However, the group represented by the above formula (L _Y2 ) is not limited to the following. In the following formulas, * represents a bonding position.

Specific examples of the group represented by formula Y1 are shown below. However, the above groups are not limited to the following specific examples. In the following formulas, * represents a bonding position.

Specific examples of the repeating unit represented by the formula Y2 are shown below. However, the said repeating unit is not limited to the following specific examples.

Specific examples of the group represented by the formula Y3 include —SO ₃ H and the like. However, the said group is not limited to a specific example.

It is preferable that the resin C2 contain a repeating unit Y.
The repeating unit containing a group represented by the formula Y1 or a group represented by the formula Y3 is a monomer containing a group represented by the formula Y1 or a monomer containing a group represented by the formula Y3 It is preferable that it is a repeating unit based on these, and it is more preferable that the said monomer contains a polymeric group.
As an aspect of the polymeric group which the said monomer contains, it is the same as that of the polymeric group which the repeating unit based on the monomer containing the group represented by said Formula X2 contains.

Specific examples of the repeating unit containing a group represented by the formula Y1 include the following repeating units. In addition, the said repeating unit is not limited to the following specific example.

It does not specifically limit as content of repeating unit Y in resin C2, 5-100 mol% is preferable with respect to all the repeating units in resin C2, and 10-100 mol% is more preferable.
The resin C2 may contain one or two or more repeating units Y. When resin C2 contains 2 or more types of repeating units Y, it is preferable that total content is in the said range.

(Repeating unit Z)
The resin C2 may contain repeating units Z other than the repeating unit X and the repeating unit Y. The aspect of the repeating unit Z is as described above.
It does not specifically limit as content of the repeating unit Z in resin C2, 0-70 mol% is preferable with respect to all the repeating units in resin C2, and 5-70 mol% is more preferable.
The resin C2 may contain one or two or more repeating units Z. When resin C2 contains 2 or more types of repeating units Z, it is preferable that total content is in the said range.

  It does not specifically limit as a weight average molecular weight of resin C2, As a polystyrene conversion value measured by GPC (Gel Permeation Chromatography) method, 7000-50000 are preferable, 7500-40000 are more preferable, and 7800-30000 are still more preferable.

The content of the resin C2 in the actinic ray-sensitive or radiation-sensitive resin composition is not particularly limited, but is 0.3 based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. -8 mass% is preferable, and 0.5-5 mass% is more preferable.
The resin C2 may be used alone or in combination of two or more. When using 2 or more types of resin C2 together, it is preferable that the total content of resin C2 in the said actinic-ray-sensitive or radiation-sensitive resin composition is in the said range.

When the actinic ray-sensitive or radiation-sensitive resin composition contains the resin C1 and the resin C2, the total content thereof is relative to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. 0.4-8 mass% is preferable, and 0.7-7 mass% is more preferable.
The mass ratio of the content of resin C2 to the content of resin C1 in the actinic ray-sensitive or radiation-sensitive resin composition (content mass ratio: content of resin C2 / content of resin C1) is 0 6-8 are preferable and 0.8-5 are more preferable.

<Resin C>
Resin C is a resin containing both of the following (i) and (ii).
(I) At least one selected from the group consisting of a repeating unit represented by Formula X1, a group represented by Formula X2, and a group represented by Formula X3.
(Ii) At least one selected from the group consisting of a group represented by the formula Y1, a group represented by the formula Y3, and a repeating unit represented by the formula Y2.
As resin C, it is preferable to contain the repeating unit X and the repeating unit Y.
In addition, the aspect of (i), (ii), repeating unit X, and repeating unit Y is as having demonstrated already.
Resin C may also contain repeating unit Z. Aspects of the repeating unit Z are as described above.

It does not specifically limit as content of the repeating unit X in resin C, 0.1-99 mol% is preferable with respect to all the repeating units in resin C, and 1-96 mol% is more preferable.
It does not specifically limit as content of repeating unit Y in resin C, 0.1-99 mol% is preferable with respect to all the repeating units in resin C, and 1-96 mol% is more preferable.
It does not specifically limit as content of the repeating unit Z in resin C, 0-50 mol% is preferable with respect to all the repeating units in resin C, and 3-50 mol% is more preferable.

The weight average molecular weight of the resin C is not particularly limited, and is preferably 6000 to 50000, more preferably 7000 to 50000, still more preferably 7500 to 40000 as a polystyrene conversion value measured by GPC (Gel Permeation Chromatography) method. Particularly preferred is 30000, and most preferred is 8,000 to 30000.
When the weight average molecular weight of the resin C is 7,000 or more, the resist film obtained by the actinic ray sensitive or radiation sensitive resin composition has more excellent water followability, and the weight average molecular weight of the resin C is The resist film obtained by the said actinic-ray-sensitive or radiation-sensitive resin composition as it is 7500 or more has the further outstanding water followability.

The content of the resin C in the actinic ray-sensitive or radiation-sensitive resin composition is not particularly limited, and is 0.4 based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. -8 mass% is preferable, and 0.6-6 mass% is more preferable.
Resin C may be used alone or in combination of two or more. When using 2 or more types of resin C together, it is preferable that the total content of resin C in the said actinic-ray-sensitive or radiation-sensitive resin composition is in the said range.

The resin C, the resin C1, and the resin C2 are preferably at least one polymer selected from the group consisting of (meth) acrylate derivatives, styrene derivatives, and allyl group-containing compounds.
In addition, it is preferable that at least one resin selected from the group consisting of the resin C1, the resin C2, and the resin C contain an aromatic ring.

The actinic ray-sensitive or radiation-sensitive resin composition contains at least one of the combination of the resin C1 and the resin C2 and the resin C. As a combination of the resin C1, the resin C2 and the resin C contained in the actinic ray-sensitive or radiation-sensitive resin composition,
Resin C; Resin C1 and Resin C2; Resin C and Resin C1; Resin C and Resin C2; Resin C1 Resin C2 and Resin C;
Etc. In addition, each resin may be used individually by 1 type, or may use 2 or more types together.
Among them, as the actinic ray-sensitive or radiation-sensitive resin composition, the resin C and at least one selected from the group consisting of the resin C1 and the resin C2 are preferable in that the more excellent effect of the present invention is obtained. It is preferable to contain.

  When the actinic ray-sensitive or radiation-sensitive resin composition contains one or more specific resins selected from the group consisting of resin C1, resin C2 and resin C, all the specific resins have the formula 3 It is preferable to contain a repeating unit derived from a monomer satisfying at least one formula selected from the group consisting of A resist film formed using an actinic ray-sensitive or radiation-sensitive resin composition in which all the specific resins satisfy the above formula has more excellent developability. The resist film particularly has better developability and water tracking. The developability and the followability to water can be evaluated by the “pattern collapse, LER, scum, development defect, water followability” evaluation method (each evaluation method described in the examples) described later.

P / Mw 0.03 0.03 (3)
Q _F × M _F /Mw≧0.35 (4)
Q _Si × M _Si /Mw≧0.15 (5)

In Formula 3, P represents the ClogP value of a monomer. The above-mentioned "monomer" intends the monomer which forms specific resin by polymerizing.
Here, the "CLogP value" is a computer-calculated value of LogP in which the distribution coefficient P in water-n-octanol is expressed by common logarithm, and is used as an index representing the degree of hydrophilicity / hydrophobicity of a substance. The CLogP of each monomer can be calculated, for example, by using Cambridge Draw's software, Chem Draw Ultra 8.0.
Moreover, Mw represents the molecular weight of the said monomer. Here, "molecular weight" intends molecular weight which can be calculated from the chemical structural formula of each monomer.

In Formula 4, Q _F represents the number of fluorine atoms per molecule of each monomer, and M _F represents the atomic weight of fluorine atoms.
Further, in the formula 5, Q _Si represents the number of silicon atoms per molecule of each monomer, and M _Si represents the atomic weight of silicon atoms.

  The specific resin more preferably contains a repeating unit derived from a monomer that satisfies the above formula (4) and the following formula (6), or the above formula (5) and the following formula (6). The resist film obtained by the actinic ray-sensitive or radiation-sensitive resin composition containing a monomer satisfying the above formula has more excellent developability. In the resist film, in particular, development residues are less likely to occur during development. In addition, the difficulty of generating the development residue can be evaluated by the "scum" evaluation method described later.

P / Mw 0.02 0.02 (6)
In Formula (6), P and Mw are the same as P and Mw in Formula (3).

  It is preferable that resin C, resin C1 and resin C2 have few impurities such as metal, and the residual monomer and / or oligomer component is preferably 0 to 10% by mass, more preferably 0 to 5% by mass 0 to 1% by mass is even more preferable. As a result, an actinic ray-sensitive or radiation-sensitive resin composition having no foreign matter in liquid and / or no change with time such as sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersion degree) is preferably in the range of 1 to 3, more preferably 1 to 2, still more preferably in terms of resolution, resist shape, sidewall of resist pattern, roughness, etc. It is in the range of 1 to 1.8, most preferably 1 to 1.5.

Commercially available products can be used as the resin C, the resin C1 and the resin C2, and they can be synthesized by a known method, for example, a radical polymerization method.
As the above synthesis method, for example, the method described in paragraph 0203 to paragraph 0210 of JP 2010-44358 A can be used, and the above contents are incorporated in the present specification.

The following resin is mentioned as a specific example of resin C, resin C1, and resin C2. In addition, the said resin is not limited to the following specific example. Table 1 also shows the molar ratio of the repeating units in each resin (each repeating unit corresponds to each from the left) and the weight average molecular weight (Mw).

In the formula, * represents a bonding position.

In the formula, * represents a bonding position.

  In the above table, "-" indicates that the monomer in the column is not contained (the same applies hereinafter).

[Optional component]
The actinic ray-sensitive or radiation-sensitive resin composition may contain components other than those described above. As components other than the above, a solvent, a basic compound, etc. are mentioned, for example.

<Solvent D>
Examples of the solvent that can be used when preparing the actinic ray-sensitive or radiation-sensitive resin composition by dissolving the components described above include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate Esters, alkyl alkoxypropionates, cyclic lactones (preferably having a carbon number of 4 to 10), monoketone compounds (preferably having a carbon number of 4 to 10) which may contain a ring, alkylene carbonates, alkyl alkoxyacetates, alkyl pyruvates, etc. Organic solvents can be mentioned.

  Specific examples of alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactic acid alkyl ester, cyclic lactone, a monoketone compound which may contain a ring, alkylene carbonate, alkyl alkoxyacetate and alkyl pyruvate , Paragraphs 0227, 0228, 0229, 0230, 0231, 0232, and 0233 in document A, the contents of which are incorporated herein. Preferred solvents also include those described in paragraph 0234 of document A, the contents of which are incorporated herein.

The above solvents may be used alone or in combination of two or more.
Moreover, 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. In addition, as a solvent which contains a hydroxyl group, and a solvent which does not contain a hydroxyl group, it describes in the 0235 paragraph and the 0236 paragraph of the literature A, respectively, and this content is included in this specification.

The mixing ratio (mass) of the hydroxyl group-containing solvent and the hydroxyl group-free solvent is 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent containing no hydroxyl group is particularly preferred in view of coating uniformity.
The solvent is preferably a mixture of two or more of propylene glycol monomethyl ether acetate.

<Basic compound>
The actinic ray-sensitive or radiation-sensitive resin composition preferably contains a basic compound in order to reduce the change in performance over time from exposure to heating. In addition, as an aspect of a basic compound, it describes in the 0238-0250 paragraph of the literature A, and this content is integrated in this specification.

Particularly preferable compounds (D) are specifically shown as the basic compounds, but the basic compounds are not limited thereto.

  The above-described basic compounds may be used alone or in combination of two or more.

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

<Surfactant>
The actinic ray-sensitive or radiation-sensitive resin composition preferably further contains a surfactant, and a fluorine-based and / or silicon-based surfactant (a fluorine-based surfactant, a silicon-based surfactant, a fluorine atom and the like) It is more preferable to contain any or two or more of surfactants having both of silicon atoms.

  When the actinic ray-sensitive or radiation-sensitive resin composition contains the above-mentioned surfactant, a pattern with less 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 give

  Specific embodiments of surfactants are described in paragraphs 0257-0262 of Document A, the contents of which are incorporated herein.

These surfactants may be used alone or in some combinations.
The amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total amount (excluding the solvent) of the actinic ray-sensitive or radiation-sensitive resin composition. 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 carboxylic acid onium salts include carboxylic acid sulfonium salts, carboxylic acid iodonium salts, and carboxylic acid ammonium salts. In particular, as a 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 preferable anion part, a C1-C30 linear, branched, monocyclic or polycyclic cyclic alkyl carboxylate anion is preferable. More preferably, anions of carboxylic acids in which part or all of these alkyl groups are substituted with a fluorine atom are preferred. The alkyl group may contain an oxygen atom. Thereby, the transparency to light of 220 nm or less is secured, the sensitivity and resolution are improved, and the density dependency and the exposure margin are improved.

<Dissolution blocking compound having a molecular weight of 3,000 or less that is decomposed by the action of an acid to increase the solubility in an alkali developer>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a dissolution inhibiting compound having a molecular weight of 3,000 or less (hereinafter referred to as "dissolution inhibiting compound") which is decomposed by the action of an acid to increase the solubility in an alkaline developer. May be contained. The dissolution inhibiting compound contains an acid degradable group such as a cholic acid derivative containing an acid degradable group described in Proceedings of SPIE, 2724, 355 (1996) as it does not reduce the permeability of 220 nm or less. Preferred are alicyclic or aliphatic compounds. As the acid decomposable group and the alicyclic structure, the same ones as those described for the resin A can be mentioned.
Specific examples of the dissolution inhibiting compound include the compounds described in paragraph 0270 of Document A, the contents of which are incorporated herein.

<Other additives>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may further contain, if necessary, a dye, a plasticizer, a photosensitizer, a light absorber, and a compound that promotes the solubility in a developer (for example, a molecular weight A phenolic compound having 1,000 or less, an alicyclic or aliphatic compound having a carboxyl group, or the like can be contained.

  The total solid content concentration in the actinic ray-sensitive or radiation-sensitive resin composition is preferably 1 to 10% by mass, more preferably 1 to 8% by mass, and still more preferably 1 to 6% by mass.

[Pattern formation method]
The pattern formation method which concerns on the embodiment of this invention contains the process of the following AC.
(A) Resist film formation process:
A step of forming an actinic ray sensitive or radiation sensitive resin composition film on a substrate using an actinic ray sensitive or radiation sensitive resin composition.
(B) Exposure step:
A step of irradiating an actinic ray-sensitive or radiation-sensitive resin composition film with an actinic ray or radiation.
(C) Development step:
A step of developing the actinic ray-sensitive or radiation-sensitive resin composition film irradiated with an actinic ray or radiation using an alkali developer.
The said pattern formation method should just contain (A)-(C), and may contain another process. Hereinafter, an aspect is demonstrated for every process.

[(A) Resist film formation process]
The resist film forming step is a step of forming an actinic ray sensitive or radiation sensitive resin composition film (resist film) on a substrate using an actinic ray sensitive or radiation sensitive resin composition.

  As a method of forming a resist film on a board | substrate, the method of apply | coating actinic-ray-sensitive or radiation-sensitive resin composition on a board | substrate is mentioned, for example. The coating method is not particularly limited, and a spin coating method, a spray method, a roller coating method, an immersion method and the like which are conventionally known can be used, and the spin coating method is preferable.

  After forming the resist film, the substrate may be heated (Prebake (PB)) as necessary. Thereby, the film from which the insoluble residual solvent has been removed can be uniformly formed. The temperature of prebaking after forming the resist film is not particularly limited, and is preferably 50 ° C to 160 ° C, and more preferably 60 ° C to 140 ° C.

The substrate on which the resist film is formed is not particularly limited, and inorganic substrates such as silicon, SiN, and SiO ₂ ; coated inorganic substrates such as SOG (Spin on Glass) etc .; semiconductor manufacturing processes such as IC (Integrated Circuit) etc. And substrates generally used in the process of manufacturing a circuit board such as a thermal head and the like, the lithography process of other photofabrication, etc. can be used.

  The thickness of the resist film is not particularly limited, and is preferably 80 nm or less.

Before forming the resist film, an antireflective film may be coated on the substrate in advance.
As the antireflective film, any of inorganic film types such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon; and organic film types consisting of a light absorber and a polymer material can be used. In addition, DUV30 series manufactured by Brewer Science, DUV-40 series, AR-2 manufactured by Shipley, AR-3, AR-5, and ARC series such as ARC29A manufactured by Nissan Chemical Industries, etc. as an organic antireflective film, etc. It is also possible to use commercially available organic antireflective coatings of

[(B) Exposure step]
The exposure step is a step of irradiating the resist film with actinic rays or radiation. The exposure can be performed by a known method, and for example, the resist film is irradiated with an actinic ray or radiation through a predetermined mask. At this time, preferably, actinic light or radiation is irradiated through the immersion liquid, but it is not limited thereto. The exposure amount can be set appropriately, and usually 10 to 60 mJ / cm ² is preferable.

The wavelength of the light source used in the exposure apparatus is not particularly limited, and light having a wavelength of 250 nm or less is preferably used. Examples thereof include KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F ₂ Excimer laser light (157 nm), EUV light (13.5 nm), electron beam and the like can be mentioned. Among these, it is preferable to use ArF excimer laser light (193 nm).

  When immersion exposure is performed, the surface of the resist film may be washed with a water-based chemical solution before exposure and / or after exposure and before heating.

  The immersion liquid is preferably a liquid which is transparent to the exposure wavelength and which has a temperature coefficient of refractive index as small as possible so as to minimize distortion of the optical image projected onto the resist film. In particular, when the exposure light source is ArF excimer laser light (wavelength: 193 nm), it is preferable to use water from the viewpoints of easy availability and easy handling in addition to the above-mentioned viewpoints.

  When water is used as the immersion liquid, additives (liquids) that increase the surface activity and reduce the surface tension of the water may be added to the water in a small proportion. It is preferable that the additive does not dissolve the resist film on the substrate and that the influence on the optical coat on the lower surface of the lens element can be ignored. Distilled water is preferable as water to be used. Furthermore, pure water filtered through an ion exchange filter or the like may be used. Thereby, distortion of the optical image projected on a resist film by mixing of an impurity can be suppressed.

  Further, a medium having a refractive index of 1.5 or more can also be used in that the refractive index can be further improved. The medium may be an aqueous solution or an organic solvent.

  The above-mentioned pattern formation method may contain an exposure process multiple times. In that case, a plurality of exposures may use the same light source or different light sources, and it is preferable to use ArF excimer laser light (wavelength: 193 nm) for the first exposure.

  After exposure, heating (baking) is preferably performed, and development (preferably rinsing) is performed. Thereby, a good pattern can be obtained. The temperature of baking is not particularly limited as long as a good pattern can be obtained, and is usually 40 ° C to 160 ° C. Baking may be performed once or plural times.

[(C) Development step]
The developing step is a step of developing the resist film irradiated with the actinic rays or radiation using an alkaline developer.
In the development step, an alkaline developer is used as follows. As an alkaline developer of the actinic ray-sensitive or radiation-sensitive resin composition, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, etc., ethylamine, n-propyl Primary amines such as amines, Secondary amines such as diethylamine and di-n-butylamine Tertiary amines such as triethylamine and methyl diethylamine Alcohol amines such as dimethylethanolamine and triethanolamine An alkaline aqueous solution of a quaternary ammonium salt such as methyl ammonium hydroxide or tetraethyl ammonium hydroxide, or a cyclic amine such as pyrrole or piperidine can be used.
Furthermore, an appropriate amount of alcohol and surfactant may be added to the above alkali developer and used.

The alkali concentration of the alkali developer is usually 0.1 to 20% by mass.
The pH of the alkaline developer is usually 10.0 to 15.0.
Furthermore, an appropriate amount of alcohol and surfactant can be added to the alkaline aqueous solution and used.
Pure water may be used as the rinse liquid, and an appropriate amount of surfactant may be added thereto.

  Further, after the development process or the rinse process, a process of removing the developing solution or the rinse solution adhering on the pattern with a supercritical fluid can be performed.

  The above pattern formation method can be applied to a method of manufacturing an electronic device. In the present specification, the “electronic device” intends a semiconductor device, a liquid crystal device, and an electric / electronic device (home appliance, media related device, optical device, communication device, etc.).

  Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, proportions, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as limited by the following examples.

Synthesis Example 1 Synthesis of Resin (C-1)
1,1,1,3,3,3-hexafluoro-2- (4-vinylphenyl) propan-2-ol (20 g) was dissolved in propylene glycol monomethyl ether acetate (40 g) to give a solution. To this solution was added 3 mol% of a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) based on the total amount of monomers. The resultant was dropwise added to propylene glycol monomethyl ether acetate (40 g) heated to 80 ° C. in a nitrogen atmosphere over 6 hours to obtain a reaction liquid. After completion of the dropwise addition, the reaction solution was stirred for 2 hours. After completion of the reaction, the reaction solution is cooled to room temperature, crystallized in 1000 mL of a methanol / water mixed solution (volume ratio 9/1), and the precipitated white powder is collected by filtration to obtain the desired resin (C-1) 12g was recovered.
The weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 9,600.
Similarly, other resins shown in Table 1 were synthesized.

Synthesis Example 2 Synthesis of Resin (1)
Under a nitrogen stream, 8.6 g of cyclohexanone was placed in a three-necked flask and heated to 80 ° C. To this, 9.8 g of 2-adamantyl isopropyl methacrylate, 4.4 g of dihydroxy adamantyl methacrylate, and 8.9 g of norbornane lactone methacrylate were added to obtain a monomer liquid. Next, a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was weighed so as to be 8 mol% with respect to the total amount of monomers, and the polymerization initiator was dissolved in 79 g of cyclohexanone. A solution was obtained. The reaction solution was obtained by dropping the polymerization initiator solution over 6 hours to the monomer solution. After completion of the dropwise addition, reaction was further carried out at 80 ° C. for 2 hours. The reaction solution was allowed to cool, and then added dropwise to a mixture of 800 mL of hexane / 200 mL of ethyl acetate over 20 minutes. The precipitated powder was collected by filtration and dried to obtain 19 g of resin (1). The weight average molecular weight of the obtained resin determined by GPC measurement was 8800 in terms of standard polystyrene, and the degree of dispersion (Mw / Mn) was 1.9.
Similarly, another resin A shown below was synthesized.
The structure of the acid decomposable resin A used in the examples is shown below. Table 2 also shows the molar ratio of repeating units in each resin (in order from the left in the structural formula), the weight average molecular weight (Mw), and the degree of dispersion (Mw / Mn).

[Preparation of actinic ray-sensitive or radiation-sensitive resin composition (resist composition)]
The components shown in Tables 3 and 4 below are dissolved in a solvent to prepare a solution having a solid concentration of 5% by mass, which is filtered through a polyethylene filter having a pore size of 0.1 μm to obtain a positive resist composition Prepared. The prepared positive resist composition was evaluated by the following method, and the results are shown in Tables 3 and 4.
The symbols in Tables 3 and 4 are as follows.
The compound B capable of generating an acid upon irradiation with an actinic ray or radiation, the resin C1, the resin C2, and the resin C correspond to those exemplified above.

[Basic compound]
N-1: N, N-dibutylaniline N-2: N, N-dihexylaniline N-3: 2, 6-diisopropylaniline N-4: tri-n-octylamine N-5: N, N- dihydroxyethyl Aniline N-6: 2,4,5-triphenylimidazole N-9: 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine [Surfactant]
W-1: Megafac F 176 (manufactured by Dainippon Ink and Chemicals, Inc., fluorine system)
W-2: Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc., fluorine-based and silicon-based)
W-3: Polysiloxane polymer KP-341 (Shin-Etsu Chemical Co., Ltd. product, silicon type)
W-4: Troysol S-366 (manufactured by Troy Chemical Co., Ltd.)
W-5: PF656 (manufactured by OMNOVA, fluorine system)
W-6: PF6320 (manufactured by OMNOVA, fluorine type)
〔solvent〕
SL-2: Propylene glycol monomethyl ether acetate SL-3: Ethyl lactate SL-4: Propylene glycol monomethyl ether SL-5: γ-butyrolactone SL-6: Propylene carbonate

[Exposure process and development process]
A composition ARC29A (made by Nissan Chemical Industries, Ltd.) for forming an organic antireflective film was coated on a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflective film of 98 nm. The prepared positive resist composition was applied onto the formed antireflective film, and baked at 130 ° C. for 60 seconds to form an 80 nm resist film. The obtained resist film-coated wafer was exposed through a 6% halftone mask having a width of 75 nm and a 1: 1 line-and-space pattern using an ArF excimer laser immersion scanner (ASTL XT1250i, NA 0.85). Ultrapure water was used as the immersion liquid. Thereafter, the exposed resist film was heated at 130 ° C. for 60 seconds. Thereafter, the resist was developed with a tetramethyl ammonium hydroxide aqueous solution (2.38 mass%) for 30 seconds, rinsed with pure water, and spin-dried to obtain a resist pattern.

[Developability evaluation]
[Developability evaluation 1: Pattern collapse]
The pattern collapse is based on an exposure dose that reproduces a 75 nm line-and-space pattern as the optimum exposure dose, and a line-and-space 1: 1 dense pattern and a line-and-space 1:10 isolated pattern when exposed at the optimal exposure dose. The line width resolved without the pattern falling down at a fine mask size was taken as the limit pattern falling line width. The smaller the value, the finer the pattern is to be resolved without falling, indicating that pattern falling is less likely to occur. In addition, "T-top" in Table 4 intends the condition where the pattern upper part becomes thick, pattern collapse generate | occur | produces, and it is intending that it was impossible to measure.
The results are shown in Tables 3 and 4.

[Developability evaluation 2: Line edge roughness (LER)]
Measure the distance from the reference line where the edge should be 50 points by using a scanning electron microscope (S-8840 manufactured by Hitachi, Ltd.) and measure the standard deviation for a range of 5 μm in the longitudinal direction of the line pattern. It calculated | required and calculated 3 (sigma). The smaller this value is, the better the performance is.
The values were evaluated according to the following criteria, and the results are shown in Tables 3 and 4. In addition, C or more is preferable practically.

A: The 3σ value was less than 5.0.
B: The 3σ value was 5.0 or more and less than 6.0.
C: 3σ value was 6.0 or more and less than 7.0.
D: The 3σ value was 7.0 or more.

[Developability evaluation 3: scum]
The development residue (scum) in a resist pattern with a line width of 75 nm was observed using a scanning electron microscope (S-4800 manufactured by Hitachi) and evaluated according to the following criteria. The results are shown in Tables 3 and 4. In addition, C or more is preferable practically.

A: No residue was generated at all.
B: A little residue was generated, but at a level at which there is no problem in practical use.
C: A considerable amount of residue was generated, but it was within the practical range.
D: Residues were severely generated.

[Developability evaluation 4: Development defect evaluation]
Using the defect inspection system KLA2360 (trade name) manufactured by KLA Tencor Co., the pixel size of the defect inspection system is 0.16 μm, and the threshold value of the substrate with the resist film subjected to the above exposure process and development process is 0.16 μm Was set to 20, measurement was performed in a random mode, development defects extracted from the difference caused by superposition of the comparative image and the pixel unit were detected, and the number of development defects per unit area (1 cm ² ) was calculated. The smaller the value of the number of development defects per unit area, the better the performance. It evaluated by the following criteria, and the result was shown in Table 3 and Table 4. In addition, C or more is preferable practically.

A: The number of development defects per unit area was less than 0.5.
B: The number of development defects per unit area was 0.5 or more and less than 0.7.
C: The number of development defects per unit area was 0.7 or more and less than 1.0.
D: The number of development defects per unit area was 1.0 or more.

[Water tracking evaluation]
The resist composition prepared above was coated on a silicon wafer and baked at 130 ° C. for 60 seconds to form a resist film of 160 nm to obtain a wafer with a resist film. Next, the obtained resist film-coated wafer was placed so that the resist film and the quartz glass substrate face each other, and pure water was filled therebetween.
In the above state, the quartz glass substrate was moved (scanned) parallel to the wafer surface, and the appearance of pure water following it was visually observed. Gradually increase the scan speed of the quartz glass substrate, and follow the water by finding the limit scan speed (unit: nm / sec) at which pure water can not follow the scan speed of the quartz glass substrate and water droplets will remain on the reverse side The sex was evaluated. As the critical scan speed is higher, water can follow the higher scan speed, indicating that the water followability on the resist film is better. The results are shown in Tables 3 and 4. In addition, 100 nm / sec or more is preferable practically.
In addition, "mass%" of the "resin C1""resinC2""resinC" column in Table 3 and Table 4 represents content with respect to a total solid.

In addition, in Table 3, as resin "C-34", resin which consists of the following repeating units was used. Moreover, the molecular weight of resin "C-34" was shown in the following table.

From the results shown in Tables 3 and 4, an actinic ray-sensitive or radiation-sensitive resin containing a combination of resin A, compound B, resin C1 and resin C2, and at least one of resin C In the pattern formation methods of Examples 1 to 37 using the composition, desired effects could be obtained. On the other hand, in the pattern formation methods of Comparative Examples 1 to 7, desired effects were not obtained.
The pattern forming method according to claim 19, wherein the actinic ray-sensitive or radiation-sensitive resin composition satisfies the relationship of claim 2, has better developability and water followability as compared with the pattern forming method according to example 17. Had.
The pattern forming method of Examples 5, 10, 11, 25 to 30 in which the actinic ray-sensitive or radiation-sensitive resin composition satisfies the relationship of claim 3 is compared with the pattern forming method of Example 1 to develop. There was no "C" evaluation in the evaluation of the property, and it had more excellent developability.
The pattern formation method of Example 2, wherein the actinic ray-sensitive or radiation-sensitive resin composition contains a resin C, and further contains at least one selected from the group consisting of a resin C1 and a resin C2 is carried out Compared with the pattern formation method of Example 1, it had more excellent developability and water followability.

Claims (32)

A resist film forming step of forming an actinic ray-sensitive or radiation-sensitive resin composition film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition;
Exposing the actinic ray-sensitive or radiation-sensitive resin composition film to an actinic ray or radiation;
Developing the actinic ray-sensitive or radiation-sensitive resin composition film irradiated with the actinic ray or radiation using an alkaline developer;
A pattern forming method containing
Resin A in which the actinic ray-sensitive or radiation-sensitive resin composition has increased solubility in an alkaline developer by the action of an acid
A compound B capable of generating an acid upon irradiation with an actinic ray or radiation;
A combination of resin C1 and resin C2, and at least one of resin C,
A pattern forming method containing
The resin C1 is
And at least one selected from the group consisting of a repeating unit represented by Formula X1, a group represented by Formula X2, and a group represented by Formula X3;
The resin C2 is
And at least one selected from the group consisting of a group represented by the formula Y1, a group represented by the formula Y3, and a repeating unit represented by the formula Y2;
The resin C is
At least one selected from the group consisting of a repeating unit represented by Formula X1, a group represented by Formula X2, and a group represented by Formula X3, and
And at least one selected from the group consisting of a group represented by the formula Y1, a group represented by the formula Y3, and a repeating unit represented by the formula Y2.

In Formula X1, L represents a single bond or a linking group, R ₁ represents a fluorine atom, or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and R _A is a hydrogen atom or Represents a monovalent substituent, and n1 represents an integer of 1 or more.
In Formula X2, L represents a single bond or a linking group, R ₂ represents a fluorine atom, an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, or -Si (R ₁₀ ) ₃ , Ar represents an aromatic hydrocarbon ring group, n2 represents an integer of 1 or more, and * represents a bonding position. R ₁₀ represents an alkyl group.
In formula X3, L represents a single bond or a linking group, R ₁₀ represents an alkyl group, n 3 represents an integer of 1 or more, and * represents a bonding position.
In Formula Y1, L represents a single bond or a linking group, R ₃ independently represents a fluorine atom, or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and R represents hydrogen Represents an atom or a monovalent substituent.
In formula Y2, R _A and R each independently represent a hydrogen atom or a monovalent substituent, and when R is a hydrogen atom, L _A represents a single bond and R is a monovalent substituent In the case of, L _A represents a linking group.
In Formula Y3, L represents a single bond or a linking group, R represents a hydrogen atom or a monovalent substituent, and * represents a bonding position. When the actinic ray-sensitive or radiation-sensitive resin composition contains one or two or more specific resins selected from the group consisting of the resin C1, the resin C2, and the resin C,
The pattern formation method according to claim 1, wherein all the specific resins contain a repeating unit derived from a monomer satisfying at least one formula selected from the group consisting of formulas 3 to 5.
P / Mw 0.03 0.03 (3)
Q _F × M _F /Mw≧0.35 (4)
Q _Si × M _Si /Mw≧0.15 (5)
In formulas 3 to 5, P represents the ClogP value of the monomer, Mw represents the molecular weight of the monomer, Q _F represents the number of fluorine atoms per molecule of the monomer, and M _F represents the atomic weight of fluorine atoms. , Q _Si represents the number of silicon atoms per the monomer molecule, M _Si represents the atomic weight of silicon atom. The pattern formation method of Claim 2 in which at least one of the said specific resin contains the repeating unit derived from the monomer which satisfy | fills Formula 4 and Formula 6, or Formula 5 and Formula 6.
Q _F × M _F /Mw≧0.35 (4)
Q _Si × M _Si /Mw≧0.15 (5)
P / Mw 0.02 0.02 (6)
In the formula 4 to 6, P represents the ClogP value of the monomer, Mw represents the molecular weight of the monomer, _{Q F} represents the number of fluorine atoms per a monomer _{molecule, Q Si} is per the monomer molecule It represents the number of silicon atoms, M _F represents the atomic weight of fluorine atoms, and M _Si represents the atomic weight of silicon atoms. The R ₁ in the repeating unit represented by the formula X1 and the R ₂ in the group represented by the formula X2 are alkyl groups substituted with three or more fluorine atoms. The pattern formation method as described in any one of these.   The R in the repeating unit represented by the formula Y2, and the R in the group represented by the group represented by the formula Y1 and the group represented by the formula Y1 are hydrogen atoms. The pattern formation method as described in a term.   R in the repeating unit represented by the formula Y2, and R in the group represented by the group represented by the formula Y1 and the group represented by the formula Y1 are each an alkyl group containing a substituent, an aryl group, or The pattern formation method as described in any one of Claims 1-4 which is an alkylamino group.   An alkyl group or an aryl group in which R in the repeating unit represented by the formula Y2, and R in the group represented by the group represented by the formula Y1 and the group represented by the formula Y1 are eliminated under basic conditions The pattern formation method of Claim 6 which is.   The resin C and the resin C2 contain a repeating unit containing two or more at least one group selected from the group consisting of a group represented by the formula Y1 and a group represented by the formula Y3. The pattern formation method as described in any one of -7.   The resin C, the resin C1, and the resin C2 are at least one polymer selected from the group consisting of (meth) acrylate derivatives, styrene derivatives, and allyl group-containing compounds. The pattern formation method as described in any one of these.   The pattern formation method according to any one of claims 1 to 9, wherein at least one resin selected from the group consisting of the resin C1, the resin C2 and the resin C contains an aromatic ring. The pattern formation method according to any one of claims 1 to 10, wherein the resin C1 and the resin C contain a repeating unit represented by Formula 7.

In the formula, R represents at least one selected from the group consisting of a trialkylsilyl group, a fluorinated alkyl group having 2 or more carbon atoms, and a tertiary alkyl group, and R _A represents a hydrogen atom or a monovalent atom And n represents an integer of 2 or more. The actinic ray-sensitive or radiation-sensitive resin composition comprises the resin C;
The pattern formation method according to any one of claims 1 to 11, comprising at least one selected from the group consisting of the resin C1 and the resin C2.   The pattern formation method according to any one of claims 1 to 12, wherein the resin A contains a repeating unit containing a lactone structure.   The pattern formation method according to any one of claims 1 to 13, wherein the actinic ray-sensitive or radiation-sensitive resin composition further contains a solvent D.   The pattern formation method as described in any one of Claims 1-14 whose film thickness of the said actinic-ray-sensitive or radiation-sensitive resin composition film | membrane is 80 nm or less.   The pattern formation method according to any one of claims 1 to 15, wherein the exposure step is a liquid immersion exposure step.   The manufacturing method of an electronic device containing the pattern formation method as described in any one of Claims 1-16. Resin A whose solubility in an alkaline developer is increased by the action of an acid,
A compound B capable of generating an acid upon irradiation with an actinic ray or radiation;
A combination of resin C1 and resin C2, and at least one of resin C,
An actinic ray-sensitive or radiation-sensitive resin composition containing
The resin C1 is
And at least one selected from the group consisting of a repeating unit represented by Formula X1, a group represented by Formula X2, and a group represented by Formula X3;
The resin C2 is
And at least one selected from the group consisting of a group represented by the formula Y1, a group represented by the formula Y3, and a repeating unit represented by the formula Y2;
The resin C is
At least one selected from the group consisting of a repeating unit represented by Formula X1, a group represented by Formula X2, and a group represented by Formula X3, and
And at least one selected from the group consisting of a group represented by the formula Y1, a group represented by the formula Y3, and a repeating unit represented by the formula Y2.

In Formula X1, L represents a single bond or a linking group, R ₁ represents a fluorine atom, or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and R _A is a hydrogen atom or Represents a monovalent substituent, and n1 represents an integer of 1 or more.
In Formula X2, L represents a single bond or a linking group, R ₂ represents a fluorine atom, an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, or -Si (R ₁₀ ) ₃ , Ar represents an aromatic hydrocarbon ring group, n2 represents an integer of 1 or more, and * represents a bonding position. R ₁₀ represents an alkyl group.
In formula X3, L represents a single bond or a linking group, R ₁₀ represents an alkyl group, n 3 represents an integer of 1 or more, and * represents a bonding position.
In Formula Y1, L represents a single bond or a linking group, R ₃ independently represents a fluorine atom, or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and R represents hydrogen Represents an atom or a monovalent substituent.
In formula Y2, R _A and R each independently represent a hydrogen atom or a monovalent substituent, and when R is a hydrogen atom, L _A represents a single bond and R is a monovalent substituent In the case of, L _A represents a linking group.
In Formula Y3, L represents a single bond or a linking group, R represents a hydrogen atom or a monovalent substituent, and * represents a bonding position. It contains one or two or more specific resins selected from the group consisting of the resin C1, the resin C2, and the resin C,
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 18, wherein all the specific resins contain a repeating unit derived from a monomer satisfying at least one formula selected from the group consisting of formulas 3 to 5. object.
P / Mw 0.03 0.03 (3)
Q _F × M _F /Mw≧0.35 (4)
Q _Si × M _Si /Mw≧0.15 (5)
In formulas 3 to 5, P represents the ClogP value of the monomer, Mw represents the molecular weight of the monomer, Q _F represents the number of fluorine atoms per molecule of the monomer, and M _F represents the atomic weight of fluorine atoms. , Q _Si represents the number of silicon atoms per the monomer molecule, M _Si represents the atomic weight of silicon atom. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 19, wherein at least one of the specific resins contains a repeating unit derived from a monomer satisfying formula 4 and formula 6, or formula 5 and formula 6, object.
Q _F × M _F /Mw≧0.35 (4)
Q _Si × M _Si /Mw≧0.15 (5)
P / Mw 0.02 0.02 (6)
In the formula 4 to 6, P represents the ClogP value of the monomer, Mw represents the molecular weight of the monomer, _{Q F} represents the number of fluorine atoms per a monomer _{molecule, Q Si} is per the monomer molecule It represents the number of silicon atoms, M _F represents the atomic weight of fluorine atoms, and M _Si represents the atomic weight of silicon atoms. The R ₁ in the repeating unit represented by the formula X1 and the R ₂ in the group represented by the formula X2 are alkyl groups substituted with three or more fluorine atoms. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above.   22. The method according to any one of claims 18 to 21, wherein R in the repeating unit represented by Formula Y2, and R in the group represented by Formula Y1 and the group represented by Formula Y3 are hydrogen atoms. The actinic ray sensitive or radiation sensitive resin composition as described in a term.   R in the repeating unit represented by the formula Y2, and R in the group represented by the group represented by the formula Y1 and the group represented by the formula Y1 are each an alkyl group, an aryl group or an alkyl group containing a substituent The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 18 to 21, which is an amino group.   An alkyl group or an aryl group in which R in the repeating unit represented by the formula Y2, and R in the group represented by the group represented by the formula Y1 and the group represented by the formula Y1 are eliminated under basic conditions The actinic ray-sensitive or radiation-sensitive resin composition according to claim 23, which is   The resin C and the resin C2 contain a repeating unit containing two or more at least one group selected from the group consisting of a group represented by the formula Y1 and a group represented by the formula Y3. Actinic-ray-sensitive or radiation-sensitive resin composition according to any one of the above.   The resin C, the resin C1, and the resin C2 are at least one polymer selected from the group consisting of (meth) acrylate derivatives, styrene derivatives, and allyl group-containing compounds. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above.   27. The actinic ray-sensitive or sensitizing agent according to any one of claims 18 to 26, wherein at least one resin selected from the group consisting of the resin C1, the resin C2 and the resin C contains an aromatic ring. Radiation-sensitive resin composition. 28. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 18 to 27, wherein the resin C1 and the resin C contain a repeating unit represented by Formula 7.

In the formula, R represents at least one selected from the group consisting of a trialkylsilyl group, a fluorinated alkyl group having 2 or more carbon atoms, and a tertiary alkyl group, and R _A represents a hydrogen atom or a monovalent atom And n represents an integer of 2 or more. Said resin C,
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 18 to 28, comprising at least one selected from the group consisting of the resin C1 and the resin C2.   The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 18 to 29, wherein the resin A contains a repeating unit containing a lactone structure.   The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 18 to 30, further comprising a solvent D. A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 18 to 31.