JP5401221B2 - Actinic ray-sensitive or radiation-sensitive composition and pattern forming method using the same - Google Patents

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive composition that is suitably used in ultra-microlithography processes such as the manufacture of VLSI and high-capacity microchips, imprint mold production processes, and other photofabrication processes. More specifically, the present invention can form a highly refined pattern using electron beam, X-ray, EUV light, etc., and can be used suitably for fine processing of semiconductor elements. In one embodiment, the present invention relates to a positive resist composition.

  In the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays, X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation.

  Conventionally, in the manufacturing process of semiconductor devices such as IC and LSI, fine processing by lithography using a photoresist composition has been performed. In recent years, with the high integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quarter micron region has been required. Along with this, there is a tendency to shorten the exposure wavelength from g-line to i-line and further to KrF excimer laser light. Furthermore, at present, in addition to excimer laser light, lithography using electron beams, X-rays, or EUV light is also being developed.

  In particular, electron beam lithography is positioned as a next-generation or next-generation pattern formation technique, and a positive resist with high sensitivity and high resolution is desired. In particular, high sensitivity is an extremely important issue for shortening the wafer processing time. However, in positive resists for electron beams, when trying to increase sensitivity, not only the resolution is lowered, but also the line edge. Roughness deteriorates, and development of a resist that satisfies these characteristics at the same time is strongly desired. Here, the line edge roughness means that when the pattern is viewed from directly above because the resist pattern and the edge of the substrate interface vary irregularly in the direction perpendicular to the line direction due to the characteristics of the resist. Say that the edge looks uneven. The unevenness is transferred by an etching process using a resist as a mask, and the electrical characteristics are deteriorated, so that the yield is lowered. Particularly in a fine region of 0.25 μm or less, improvement of line edge roughness is a very important issue. High sensitivity, high resolution, good pattern shape, and good line edge roughness are in a trade-off relationship, and how to satisfy these simultaneously is very important.

  Further, in lithography using X-rays or EUV light, it is also important to achieve both high sensitivity and high resolution, and these solutions are necessary.

  As a resist suitable for a lithography process using such electron beam, X-ray or EUV light, a chemically amplified resist using an acid catalyst reaction is mainly used from the viewpoint of high sensitivity. As a main component, it consists of a phenolic polymer (hereinafter abbreviated as a phenolic acid-decomposable resin) that is insoluble or hardly soluble in an aqueous alkaline solution and becomes soluble in an aqueous alkaline solution by the action of an acid, and an acid generator. Chemically amplified resist compositions are effectively used.

  However, in the finer patterning formation of 100 nm or less, since the resin compound as described above has a large dissolution unit and a molecular weight distribution and a composition ratio distribution, sufficient line edge roughness and resolution can be obtained. It was difficult to get.

  As a method for solving these problems, an acid-decomposable compound having a low molecular weight different from that of conventional resins [for example, phenolic compound derivatives having a specific structure (for example, see Patent Documents 1 and 4), having a specific structure. Calixarene (for example, see Patent Document 2), calix resorcinarene (for example, see Patent Document 3), phenolic dendrimer having calixresorcinarene as a mother nucleus (for example, see Patent Document 3), torquesen derivative (for example, Patent Document 5) And the like] are known as resist compositions. However, even if these low molecular weight compounds are used, it is difficult to say that a sufficient improvement effect is obtained as compared with conventional resin compounds, and further improvement is desired.

  On the other hand, it is known that a specific photoacid generator is effective as a method for improving line edge roughness and resolving power (see, for example, Patent Document 6), but the source of the effect is not clear. There is also no known example of use in combination with the low molecular weight compounds described.

  In addition, with the recent miniaturization of patterns, the thinning of resists is progressing, and improving the edging resistance of resists is also an important issue.

JP-A-10-83073 JP-A-10-120610 JP-A-10-310545 JP 2000-305270 A JP 2008-76850 A JP 2005-97254 A

  An object of the present invention is to improve resolution, fineness of line edge roughness and etching resistance, and to improve sensitivity and pattern shape in order to improve performance in microfabrication of semiconductor elements using high energy rays, X-rays, electron beams or EUV light. An object is to provide an excellent actinic ray-sensitive or radiation-sensitive composition and a pattern forming method using the same.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. The present invention is as follows.

[1] A low molecular weight compound (1) having an acid-decomposable group (G) that decomposes by the action of an acid and promotes solubility in an alkali developer, and a volume by irradiation with actinic rays or radiation. 305. Actinic ray-sensitive or radiation-sensitive composition comprising a compound (2) that generates ³ or more acids.

[2] The actinic ray-sensitive or radiation-sensitive composition according to [1], wherein the compound (2) is represented by the following general formula (2-1) or (2-2): object.

In general formula (2-1),
Ar represents an aromatic ring, and may further have a substituent in addition to the — (AB) group.

  n represents an integer of 1 or more, A represents a single bond or a divalent linking group, and B represents a group having a hydrocarbon group.

  When n is 2 or more, a plurality of — (AB) groups may be the same or different.

Q ⁻ represents an anion having a pKa of a conjugate acid of 6 or less, and M ⁺ represents an organic onium ion.

In general formula (2-2),
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.

  J represents a single bond or a linear, branched or cyclic alkylene group which may contain ether oxygen, an arylene group, or a group consisting of a combination of these groups, and the group to be combined is an oxygen atom. May be connected.

  L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.

  E represents a group having a ring structure.

  x represents an integer of 1 to 20, and y represents an integer of 0 to 10.

Q ⁻ and M ⁺ have the same meanings as those in General Formula (2-1).

[3] The actinic ray-sensitive or radiation-sensitive composition according to [2], wherein the general formula (2-2) is the following general formula (2-3).

  In the formula, each symbol has the same meaning as each symbol in the general formulas (2-1) and (2-2).

  [4] The actinic ray according to [2] or [3], wherein in General Formula (2-1) or General Formula (2-3), B is a group having a hydrocarbon group having 4 or more carbon atoms. Or radiation sensitive compositions.

  [5] In General Formula (2-1) or General Formula (2-3), B is a group having a hydrocarbon group containing a tertiary or quaternary carbon atom having 4 or more carbon atoms, [2] Or the actinic-ray-sensitive or radiation-sensitive composition as described in [3].

  [6] The actinic ray according to [2] or [3], wherein, in the general formula (2-1) and the general formula (2-3), B is a group having a cyclic hydrocarbon having 4 or more carbon atoms. Or radiation sensitive compositions.

  [7] Any one of [1] to [6], wherein the low molecular compound (1) further has a solubilizing group (S) that promotes solubility in an alkaline developer. The actinic ray-sensitive or radiation-sensitive composition as described.

[8] The actinic ray-sensitive material according to any one of [1] to [7], wherein the low molecular compound (1) is a compound represented by the following general formula (1-1): Radiation sensitive composition.

In formula (1-1), W is an (a + b) -valent organic group, Y ₁ and Y ₂ are each independently a single bond or a divalent linking group, and G is decomposed by the action of an acid to form an alkali developer. An acid-decomposable group that promotes solubility, S is a solubilizing group that promotes solubility in an alkaline developer, and a and b each independently represent an integer of 1 to 30. When there are a plurality of groups in each parenthesis, the groups in the plurality of parentheses may be the same or different.

[9] A pattern forming method comprising forming a film using the actinic ray-sensitive or radiation-sensitive composition according to any one of [1] to [8], and exposing and developing the film.
[10] The pattern forming method according to [9], wherein the exposure is performed using X-rays, electron beams, or EUV.

  According to the present invention, in particular, a positive resist having excellent resolution, line edge roughness and etching resistance, and high sensitivity and good pattern shape in an ultrafine region, particularly in electron beam, X-ray or EUV light lithography. An actinic ray-sensitive or radiation-sensitive composition suitable as a composition, and a pattern forming method using the composition can be provided.

Hereinafter, the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, “exposure” in the present specification is represented not only by exposure to deep ultraviolet rays, X-rays, EUV light and the like, but also by particle beams such as electron beams and ion beams, unless otherwise specified, such as mercury lamps and excimer lasers. Drawing is also included in the exposure.

  Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited to the following embodiments, and is based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. It should be understood that modifications, improvements, and the like that are appropriately added to the following embodiments also fall within the scope of the present invention.

The present invention provides a low molecular weight compound (1) having a molecular weight of 500 to 5000 having an acid decomposable group (G) that is decomposed by the action of an acid to change the solubility in an alkali developer, and irradiation with actinic rays or radiation. relates actinic ray-sensitive or radiation-sensitive composition characterized by containing a compound capable of generating a volumetric 305A ³ or more acid (2), below, compounds capable of generating an acid (2), a low molecular compound Details will be described in the order of (1).

[Compound that generates acid (1)]
The compound that generates acid upon irradiation with actinic rays or radiation used in the present invention (hereinafter also referred to as “acid generator”) is a compound that generates an acid having a volume of 305 to ³ or more upon irradiation with actinic rays or radiation. Here, “the volume of the acid” means the volume of the region occupied by the van der Waals sphere based on the van der Waals radius of the atoms constituting the acid. Specifically, the “acid volume” is a volume calculated as follows. That is, first, the most stable conformation of the acid is determined by molecular force field calculation using the MM3 method. Thereafter, the van der Waals volume is calculated for this most stable conformation by molecular orbital calculation using the PM3 method. The van der Waals volume is defined as “acid volume”.

Acid generator used in the present invention, the volume of the acid generated upon irradiation with an actinic ray or radiation, but may be any so long 305A ³ or more as determined by the above method, a preferred embodiment is What is represented by the following general formula (2-1) or (2-2) can be mentioned.

  In General Formula (2-1), Ar represents an aromatic ring, and may further have a substituent in addition to the — (AB) group. n represents an integer of 1 or more.

A represents a single bond or a divalent linking group. Preferable examples of the divalent linking group represented by A include an alkylene group, —O—, —S—, —C (═O) —, —S (═O) —, —S (═O) _2. Any one selected from — and —OS (═O) ₂ — or a combination of two or more can be mentioned.

B represents a group having a hydrocarbon group, preferably having 1 to 30 carbon atoms, and more preferably 4 to 30 carbon atoms. B particularly preferably represents a group having a hydrocarbon group having 4 to 30 carbon atoms and containing a tertiary or quaternary carbon atom. When n is 2 or more, a plurality of — (AB) groups may be the same or different.
Q ⁻ and M ⁺ have the same meanings as those in General Formula (2-2), and details will be described later.

The aromatic ring represented by Ar is preferably an aromatic ring having 6 to 30 carbon atoms, and may further have a substituent in addition to the — (AB) group.
Specifically, benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acetaphthalene ring, phenanthrene ring, anthracene ring, naphthacene ring, pentacene ring, chrysene ring, Triphenylene ring, indene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine Ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthri Down ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring, phenazine ring, and the like. Of these, a benzene ring, a naphthalene ring and an anthracene ring are preferable, and a benzene ring is more preferable, from the viewpoint of achieving both improved roughness and high sensitivity.

  When the aromatic ring further has a substituent other than-(AB) group, examples of the substituent include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, methoxy group , Alkoxy groups such as ethoxy group, tert-butoxy group, aryloxy groups such as phenoxy group, p-tolyloxy group, alkylthioxy groups such as methylthioxy group, ethylthioxy group, tert-butylthioxy group, phenylthioxy group, p- Arylthiooxy groups such as tolyltyoxy group, alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, dodecyl group, Linear and branched alkyl groups such as 2-ethylhexyl group, vinyl An alkenyl group such as a propenyl group and a hexenyl group, an alkynyl group such as an acetylene group, a propynyl group and a hexynyl group, an aryl group such as a phenyl group and a tolyl group, an acyl group such as a benzoyl group, an acetyl group and a tolyl group, a hydroxy group, A carboxy group, a sulfonic acid group, etc. are mentioned. Among these, a straight chain alkyl group and a branched alkyl group are preferable from the viewpoint of improving roughness.

  A preferably has a small number of atoms from the viewpoint of resolution and roughness. A is preferably a single bond, —O—, or —S—, and particularly preferably a single bond.

  Examples of the hydrocarbon group in the group having a hydrocarbon group having 4 to 30 carbon atoms including a tertiary or quaternary carbon atom represented by B include an acyclic hydrocarbon group or a cyclic aliphatic group. It is done.

  Examples of the acyclic hydrocarbon group having 4 to 30 carbon atoms including tertiary or quaternary carbon atoms include t-butyl group, t-pentyl group, neopentyl group, s-butyl group, isobutyl group, and isohexyl group. 3,3-dimethylpentyl group, 2-ethylhexyl group and the like. The acyclic hydrocarbon group is more preferably one having 5 to 20 carbon atoms. The acyclic hydrocarbon group may have a substituent.

  Examples of the cycloaliphatic group having 4 to 30 carbon atoms include a cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, Examples include decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group, and pinenyl group. More preferably, the cyclic aliphatic group has 5 to 20 carbon atoms. The cyclic aliphatic group may have a substituent.

When the acyclic hydrocarbon group or cyclic aliphatic group has a substituent, examples of the substituent include halogen groups such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a methoxy group, an ethoxy group Group, alkoxy groups such as tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; alkylthioxy groups such as methylthioxy group, ethylthioxy group and tert-butylthioxy group; phenylthioxy group and p-tolyloxy group Arylthiooxy group such as methoxycarbonyl group, butoxycarbonyl group, etc .; aryloxycarbonyl group such as phenoxycarbonyl group; acetoxy group; methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group , Dodecyl group, 2-ethylhexyl group, etc. Groups, branched alkyl groups; cyclic alkyl groups such as cyclohexyl groups; alkenyl groups such as vinyl groups, propenyl groups, and hexenyl groups; alkynyl groups such as acetylene groups, propynyl groups, and hexynyl groups; and aryl groups such as phenyl groups and tolyl groups A hydroxy group, a carboxy group, a sulfonic acid group, a carbonyl group and the like. Among these, a straight chain alkyl group and a branched alkyl group are preferable from the viewpoint of achieving both roughness improvement and high sensitivity.
Specific examples of such a group having a cycloaliphatic group or an acyclic hydrocarbon group include the following. In addition, * in a formula represents the coupling | bond part with A (when A is a single bond, Ar).

Among the above, the following structure is more preferable.

As the group containing a tertiary or quaternary carbon atom represented by B and having a hydrocarbon group having 4 or more carbon atoms, a cyclic aliphatic group is preferable from the viewpoint of resolution and roughness. Among the cycloaliphatic groups, a cycloalkyl group, an adamantyl group, and a norbornyl group are preferable, a cycloalkyl group is more preferable, and a cyclohexyl group is most preferable among the cycloalkyl groups from the viewpoint of improving roughness.
n represents an integer of 1 or more, and from the viewpoint of improving roughness, it is preferably 2 or more and 5 or less, more preferably 2 or more and 4 or less, and most preferably n = 3.
From the viewpoint of improving the roughness, the — (AB) group preferably substitutes at least one o position relative to the substitution position of Q ⁻ , and more preferably substitutes two o positions.

Next, general formula (2-2) is demonstrated.
In General Formula (2-2), each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
J represents a single bond or a linear, branched or cyclic alkylene group which may contain ether oxygen, an arylene group, or a group consisting of a combination of these groups, and the group to be combined is an oxygen atom. May be connected.

  The alkylene group represented by J is preferably a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms (for example, methylene, ethylene, propylene, 1,4-cyclohexene). And a part or all of hydrogen atoms bonded to carbon may be substituted with fluorine atoms. The arylene group represented by J is preferably an arylene group having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms (for example, phenylene or naphthylene), and a part of hydrogen atoms bonded to carbon or All may be substituted with fluorine atoms. These alkylene groups and / or arylene groups may be used alone or in combination. In this case, these alkylene groups and / or arylene groups can also be combined via an oxygen atom.

L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
E represents a group having a ring structure.
x represents an integer of 1 to 20, and preferably 1 to 4. y represents an integer of 0 to 10, preferably 0 to 3.

  Xf is a fluorine atom or an alkyl group substituted with at least one fluorine atom. As this alkyl group, a C1-C10 thing is preferable and a C1-C4 thing is more preferable. The alkyl group substituted with a fluorine atom is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specifically, Xf is preferably a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F _{17, CH 2 CF 3, CH} 2 CH 2 CF 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F ₉ or CH ₂ CH ₂ C ₄ F ₉ . Among these, a fluorine atom or CF ₃ is preferable, and a fluorine atom is most preferable.

In General Formula (2-2), each of R ₁ and R ₂ is a group selected from a hydrogen atom, a fluorine atom, an alkyl group, and an alkyl group substituted with at least one fluorine atom. The alkyl group which may be substituted with a fluorine atom is preferably an alkyl group having 1 to 4 carbon atoms. Moreover, as an alkyl group substituted by the fluorine atom, a C1-C4 perfluoroalkyl group is especially preferable. Specifically, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH _{2 CH 2 CF 3, CH 2 C} 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F 9 or _CH 2 _CH 2 _{C 4} F ₉ is mentioned, and among them, CF ₃ is preferable.

Examples of the divalent linking group represented by L, such, -COO -, - OCO -, - CO -, - O -, - S -, - SO -, - SO 2 -, - N (R) - ( Here, R is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Or a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms.), An alkylene group, a cycloalkylene group, an alkenylene group, and combinations thereof. Among these, —COO—, —OCO—, —CO—, —O—, —S—, —SO— or —SO ₂ — is preferable, and —COO—, —OCO— or —SO ₂ — is more preferable.

  In General Formula (2-2), E represents a group having a ring structure. Examples of E include an alicyclic group, an aryl group, and a group having a heterocyclic structure.

  The alicyclic group as E may have a monocyclic structure or a polycyclic structure. The alicyclic group having a monocyclic structure is preferably a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group. The alicyclic group having a polycyclic structure is preferably a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. In particular, when an alicyclic group having a bulky structure of 6 or more members is adopted as E, diffusibility in the film in the PEB (post-exposure heating) step is suppressed, and the resolution and EL (exposure latitude) are further improved. It becomes possible to make it.

  The aryl group as E is, for example, a benzene ring, naphthalene ring, phenanthrene ring or anthracene ring.

  The group having a heterocyclic structure as E may have aromaticity or may not have aromaticity. The heteroatom contained in this group is preferably a nitrogen atom or an oxygen atom. Specific examples of the heterocyclic structure include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, a pyridine ring, a piperidine ring, and a morpholine ring. Among these, a furan ring, a thiophene ring, a pyridine ring, a piperidine ring, and a morpholine ring are preferable.

E may have a substituent. Examples of the substituent include an alkyl group (which may be linear, branched or cyclic, preferably 1 to 12 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), a hydroxy group, an alkoxy group. Groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamide groups and sulfonic acid ester groups.
Preferred examples of E include those represented by the following formula.

In the formula, Ar, A and B have the same meanings as described in the general formula (2-1).
In General Formula (2-1) and General Formula (2-2), Q ⁻ represents an anion having a pKa of the conjugate acid (QH) of 6 or less. Here, pKa means an acid dissociation constant in water (25 ° C.).
Q ^- by a preferred embodiment of the anion represented include the following anions.

In the formula, Rf _{1 to} Rf ₆ each independently represents a linear, branched or cyclic alkyl group optionally having an ether bond having 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group is preferably a fluorinated alkyl group substituted with one or more fluorine atoms, more preferably a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.
Q ⁻ is more preferably a sulfonate anion.

Hereinafter, examples of the acid having a volume of 305 to ³ or more generated by decomposition of the acid generator of the present invention upon irradiation with actinic rays or radiation will be described, but the present invention is not limited thereto.

Each of these examples is accompanied by a calculated volume value. This value was obtained as follows using “WinMOPAC” manufactured by Fujitsu Limited. That is, first, the chemical structure of the acid according to each example was input. Next, using this structure as an initial structure, the most stable conformation of each acid was determined by molecular force field calculation using the MM3 method. Thereafter, molecular orbital calculation using the PM3 method was performed for these most stable conformations to calculate the “accessible volume” of each acid.

In addition, the volume of the acid is preferably 350 ³ or more, and more preferably 400 ³ or more. The volume is preferably 2000 ³ or less, more preferably 1500 ³ or less. If this volume is excessively large, the sensitivity may be lowered and the solubility of the coating solvent may be reduced.

In the general formula (2-1) and the general formula (2-2), M ⁺ represents an organic onium ion.
Examples of the organic onium ion (counter cation) represented by M ⁺ include onium ions such as iodonium, sulfonium, phosphonium, diazonium, ammonium, pyridinium, quinolinium, acridinium, oxonium, selenonium, and arsonium. Preferable examples include onium ions such as iodonium, sulfonium, phosphonium, diazonium, quinolinium, and acridinium.

  Further, for example, onium ions of onium salts of Group 15 to 17 elements described in JP-A-6-184170, etc. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Diazonium ions of diazonium salts described in Bal etal, Polymer, 21, 423 (1980), US Pat. Nos. 4,069,055, 4,069,056, Re 27,992 , Ammonium ions of ammonium salts described in JP-A-3-140140 and the like; C. Necker et al., Macromolecules, 17, 2468 (1984), C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat. Nos. 4,069,055, 4,069,056, JP-A-9-202873, and the like. J. et al. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent Nos. 104,143, 339,049, 410,201, JP-A-2-150848, JP-A-2-296514. Iodonium ions of iodonium salts described in J. et al. V. Crivello et al, Polymer J. et al. 17, 73 (1985), J. MoI. V. Crivello et al. J. et al. Org. Chem. 43, 3055 (1978); R. Watt et al. PolymerSci. , Polymer Chem. Ed. , 22, 1789 (1984), J. Am. V. Crivello et al., Polymer Bull. 14, 279 (1985), J. Am. V. Crivello et al, Macromolecules, 14 (5), 1141 (1981), J. MoI. V. Crivello et al. PolymerSci. , Polymer Chem. Ed. , 17, 2877 (1979), European Patent Nos. 370,693, 161,811, 410,201, 339,049, 233,567, 297,443, 297,442, U.S. Pat.Nos. 3,902,114, 4,933,377, 4,760,013, 4, 734,444, 2,833,827, German Patent 2,904,626, 3,604,580, 3,604,581 , Sulfonium ions of sulfonium salts described in JP-A-7-28237, 8-27102 and the like, quinolinium ions of quinolinium salts described in JP-A-9-221652, and the like. V. Crivello et al., Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al. PolymerSci. , Polymer Chem. Ed. , 17, 1047 (1979), etc., selenonium ions of selenonium salts, C.I. S. Wenetal, Teh, Proc. Conf. Rad. Examples include, but are not limited to, cations such as arsonium ions of arsonium salts described in Curing ASIA, p478 Tokyo, Oct (1988).

Moreover, as said counter cation, the cation of the structure of following formula (II)-(VII) is mentioned preferably, for example.

In the formulas (II) to (VII), R ^{1 to} R ³ each independently represents an aryl group, and R ^{4 to} R ⁶ each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydrocarbon. It represents a cyclic group or a heterocyclic group, the R ⁷ to R ¹¹ each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydrocarbon group, heterocyclic group, an alkoxy group or an aryloxy group, R ¹² to to R ¹⁷ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group.

The alkyl group for R ^{4 to} R ¹¹ preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 8 carbon atoms, and is linear. Or may have a substituent.
The alkenyl group represented by R ^{4 to} R ¹¹ preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 8 carbon atoms, and further has a substituent. You may have.
The alkynyl group represented by R ^{4 to} R ¹¹ preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 8 carbon atoms, and further has a substituent. You may have.

The aryl group for R ^{1 to} R ¹¹ preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 10 carbon atoms, and further has a substituent. You may have.
The hydrocarbon ring group of R ^{4 to} R ¹¹ preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, particularly preferably 3 to 10 carbon atoms, and further substitution It may have a group.
The heterocyclic group of R ^{4 to} R ¹¹ preferably has 4 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, particularly preferably 4 to 10 carbon atoms, and further a substituent. You may have. Moreover, as a hetero atom contained in a heterocyclic group, it is preferable that they are a nitrogen atom, an oxygen atom, or a sulfur atom.

The alkoxy group of R ^{7 to} R ¹¹ is preferably an alkoxy group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 8 carbon atoms. Further, the alkoxy group may have a substituent described later, and the alkyl part of the alkoxy group may be an alkenyl group, an alkynyl group, a hydrocarbon ring group, or a non-aromatic heterocyclic group.
The aryloxy group for R ^{7 to} R ¹¹ is preferably an aryloxy group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 10 carbon atoms. The aryloxy group may have a substituent described later, and the aryl moiety of the aryloxy group may be an aromatic heterocyclic group.

In formula (III), R ² and R ³ may be bonded to form a ring if possible.
In formula (IV), two or more of R ^{4 to} R ⁶ may be combined to form a ring, if possible. Further, at least one of R ⁴ to R ^6, a compound having at least one R ⁴ to R ⁶ of another compound represented by Formula (IV), the bound structure through a single bond or a linking group There may be.
In formula (V), two or more of R ^{7 to} R ¹⁰ may combine to form a ring, if possible.

In formula (VI), two or more of R ^{11 to} R ¹⁴ may be combined to form a ring, if possible.

In formula (VII), R ^{15 to} R ¹⁷ may be combined with each other to form a ring, if possible.

The substituent that the alkyl group, alkenyl group, alkynyl group, aryl group, hydrocarbon group, heterocyclic group, alkoxy group, or aryloxy group may have is a monovalent nonmetallic atomic group other than hydrogen. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkyl groups, aryl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups. Group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N- Arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarba Yloxy group, N, N- dialkylcarbamoyl group, N, N- di-arylcarbamoyloxy, N- alkyl -N- arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group,
Acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′- Diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group Group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonyl An amino group, an N-aryl-N-alkoxycarbonylamino group, an N-aryl-N-aryloxycarbonylamino group,
Formyl group, acyl group, carboxyl group and its conjugate base group (hereinafter referred to as carboxylate), alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N- Arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base Group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-dia Sulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N - diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group, N- acylsulfamoyl group and a conjugate base group, N- alkylsulfonylsulfamoyl group _{(-SO 2 NHSO 2 (alkyl)} ) And its conjugate base group, N-arylsulfonylsulfamoyl group (—SO ₂ NHSO ₂ (aryl)) and its conjugate base group, N-alkylsulfonylcarbamoyl group (—CONHSO ₂ (alkyl)) and its conjugate base group, An N-arylsulfonylcarbamoyl group (—CONHSO ₂ (aryl)) and its conjugate base group,
Silyl group, alkoxysilyl group (—Si (Oalkyl) ₃ ), aryloxysilyl group (—Si (Oaryl) ₃ ), hydroxysilyl group (—Si (OH) ₃ ) and its conjugate base group, phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonato group), dialkylphosphono group (—PO ₃ (alkyl) ₂ ), diarylphosphono group (—PO ₃ (aryl) ₂ ), alkylarylphosphono A group (—PO ₃ (alkyl) (aryl)), a monoalkylphosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), a monoarylphosphono group (— PO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphite Hona preparative group), phosphonooxy group (-OPO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonatooxy group), dialkyl Nookishi group _{(-OPO 3 (alkyl) 2)} , diaryl phosphono group _{(-OPO 3 (aryl) 2)} , alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl phosphonooxymethyl Group (—OPO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonatoxy group), monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter, An arylphosphonatoxy group), a cyano group, and a nitro group. These substituents may be further substituted with the above substituents, and may form a ring if possible.

R ^{12 to} R ¹⁷ each independently represents a hydrogen atom, a halogen atom or a monovalent organic group.
Examples of the halogen atom represented by R ^{12 to} R ¹⁷ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom, a chlorine atom, or a bromine atom is preferable.

Examples of the monovalent organic group of R ^{12 to} R ¹⁷ include a hydroxyl group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydrocarbon ring group, a heterocyclic group, an alkoxy group, an aryloxy group, an acyl group, and an alkoxycarbonyl group. , An acyloxy group, —SO ₃ —R ^a , —NR ^b R ^c , a cyano group, —SiR ^d R ^e R ^f , —SOR ^g , —SO ₂ R ^g , a nitro group, and R ^a represents ^a hydrogen atom, an alkyl Group, alkenyl group, alkynyl group, aryl group, arylalkyl group, alkali metal atom or quaternary ammonium, R ^b , R ^c and R ^g are each independently an alkyl group, alkenyl group, alkynyl group, aryl group, It represents a hydrocarbon ring group or a heterocyclic group, in each of R ^d to R ^f independently represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydrocarbon group, heterocyclic group, Al Alkoxy represents a group, or an aryloxy group.

The alkyl group, alkenyl group, alkynyl group, aryl group, hydrocarbon ring group, heterocyclic group, alkoxy group and aryloxy group in R ^{12 to} R ^{17 have} the same meanings as those in R ^{7 to} R ¹¹ , and preferred ranges are also included. It is the same. Moreover, these groups may have the said substituent.
As the acyl group or alkoxycarbonyl group in R ^{12 to} R ¹⁷ , the carbon number on the carbon chain side is preferably 1 to 30, particularly preferably 1 to 12, and linear. May have the substituent.
The acyloxy group in R ^{12 to} R ¹⁷ preferably has 1 to 30 carbon atoms, particularly preferably 1 to 12 carbon atoms, and may be linear or have the above substituent. .

The R ^a in -SO ₃ -R ^a in R ¹² to R ^17, a hydrogen atom, the may have a substituent alkyl group which may have a substituent the aryl group, a lithium atom , Sodium atom or potassium atom.
The alkyl group, alkenyl group, alkynyl group, aryl group, hydrocarbon ring group and heterocyclic group in R ^b and R ^c in —NR ^b R ^c have the same meanings as those in R ^{7 to} R ¹¹ , and are preferable. The range is the same. Moreover, these groups may have the said substituent.

The alkyl group, alkenyl group, alkynyl group, aryl group, hydrocarbon ring group, heterocyclic group, alkoxy group and aryloxy group in R ^{d to} R ^f in —SiR ^d R ^e R ^f are the above R ^{7 to} R ^11. The preferred ranges are also the same. Moreover, these groups may have the said substituent.

The alkyl group, alkenyl group, alkynyl group, aryl group, hydrocarbon ring group and heterocyclic group in R ^g in —SOR ^g or —SO ₂ R ^g have the same meanings as those in R ^{7 to} R ¹¹ , The preferable range is also the same. Moreover, these groups may have the said substituent.
As a specific example of the counter cation represented by the general formulas (II) to (VII), for example, a counter cation having a structure represented by the following Ca-1 to Ca-41 can be preferably exemplified.

In addition, from the viewpoint of outgas suppression, preferable organic onium ions include cations having the structure of the following general formula (VIII).

In general formula (VIII),
R ^{1 to} R ¹³ each independently represent a hydrogen atom or a substituent, and at least one of R ^{1 to} R ¹³ is a substituent containing an alcoholic hydroxyl group.
Z is a single bond or a divalent linking group.

  The alcoholic hydroxyl group in the present invention represents a hydroxyl group bonded to a carbon atom of an alkyl group.

When R ^{1 to} R ¹³ are substituents containing an alcoholic hydroxyl group, R ^{1 to} R ¹³ are preferably groups represented by —W—Y. Y is an alkyl group substituted with a hydroxyl group, and W is a single bond or a divalent linking group.

The alkyl group of Y is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl Group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group Preferably ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group and sec-butyl group, more preferably ethyl group, propyl group and isopropyl group. Y particularly preferably contains a —CH ₂ CH ₂ OH structure.

  The divalent linking group represented by W is not particularly limited, and examples thereof include an alkoxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an acylamino group, an aminocarbonylamino group, Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, alkylthio group, arylthio group, sulfamoyl group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxy Examples thereof include a divalent group in which an arbitrary hydrogen atom in a monovalent group such as a carbonyl group, an alkoxycarbonyl group, or a carbamoyl group is replaced with a single bond.

  W is preferably a single bond, an alkoxy group, an acyloxy group, an acylamino group, an alkyl and arylsulfonylamino group, an alkylthio group, an alkylsulfonyl group, an acyl group, an alkoxycarbonyl group, and any hydrogen atom in the carbamoyl group replaced with a single bond. It is a divalent group, more preferably a divalent group in which any hydrogen atom in a single bond, acyloxy group, alkylsulfonyl group, acyl group or alkoxycarbonyl group is replaced with a single bond.

When R ^{1 to} R ¹³ are substituents containing an alcoholic hydroxyl group, the number of carbon atoms contained is preferably 2 to 10, more preferably 2 to 6, and particularly preferably 2 to 4. .
The substituent containing an alcoholic hydroxyl group as R ^{1 to} R ¹³ may have two or more alcoholic hydroxyl groups. The number of alcoholic hydroxyl groups having a substituent containing an alcoholic hydroxyl group as R ^{1 to} R ¹³ is 1 to 6, preferably 1 to 3, and more preferably 1. preferable.
The number of alcoholic hydroxyl groups contained in the compound represented by the general formula (VIII) is 1 to 10 in total, preferably 1 to 6, more preferably 1 in total for R ^{1 to} R ^13. It is three from.

When R ^{1 to} R ¹³ do not contain an alcoholic hydroxyl group, R ^{1 to} R ¹³ are each independently a hydrogen atom or a substituent, and any substituent may be used without any particular limitation. Atoms, alkyl groups (including cycloalkyl groups, bicycloalkyl groups, and tricycloalkyl groups), alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkynyl groups, aryl groups, and heterocyclic groups (referred to as heterocyclic groups) Cyano group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group ( Anilino group), ammonio group, acylamino group, aminocarbonyl group Group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and aryl Sulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino Group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (—B (OH) ₂ ), phosphato group (—OPO (OH) ₂ ), sulfato group (—OSO ₃ H), and other known ones Substituents are mentioned as examples.

In addition, two adjacent R ^{1 to} R ¹³ may be combined to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring. These may be further combined to form a polycyclic fused ring. For example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine Ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, Phenanthridine ring, acridine ring, Ntororin ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring and a phenazine ring.) May also be formed.

When R ^{1 to} R ¹³ do not contain an alcoholic hydroxyl group, R ^{1 to} R ¹³ are preferably a hydrogen atom or a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group ( Cycloalkenyl group, bicycloalkenyl group), alkynyl group, aryl group, cyano group, carboxyl group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, Aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, alkylthio group, arylthio group, sulfamoyl group, alkyl and arylsulfonyl group, aryloxycarbonyl group, alkoxycarbonyl group A carbamoyl group, an imido group, a silyl group, a ureido group.

When R ^{1 to} R ¹³ do not contain an alcoholic hydroxyl group, R ^{1 to} R ¹³ are more preferably a hydrogen atom or a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), a cyano group. , Alkoxy group, acyloxy group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkyl and arylsulfonylamino group, alkylthio group, sulfamoyl group, alkyl and arylsulfonyl group, alkoxycarbonyl group and carbamoyl group.

Further, when R ^{1 to} R ¹³ do not contain an alcoholic hydroxyl group, R ^{1 to} R ¹³ are particularly preferably a hydrogen atom or an alkyl group (including a cycloalkyl group, a bicycloalkyl group and a tricycloalkyl group), a halogen atom, An alkoxy group;

In general formula (VIII), at least one of R ^{1 to} R ¹³ contains an alcoholic hydroxyl group, and preferably at least one of R ^{9 to} R ¹³ contains an alcoholic hydroxyl group.

Z represents a single bond or a divalent linking group, and examples of the divalent linking group include an alkylene group, an arylene group, a carbonyl group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamide group, an ether group, and a thioether. Group, amino group, disulfide group, acyl group, alkylsulfonyl group, —CH═CH—, —C≡C—, aminocarbonylamino group, aminosulfonylamino group, etc., which may have a substituent. These substituents are the same as the substituents shown for R ^{1 to} R ¹³ above. Z preferably has a single bond, alkylene group, arylene group, ether group, thioether group, amino group, —CH═CH—, —C≡C—, aminocarbonylamino group, aminosulfonylamino group, etc. A substituent, more preferably a single bond, an ether group or a thioether group, particularly preferably a single bond.
Specific examples of the onium ion represented by the general formula (VIII) are shown below, but are not limited thereto.

The addition amount of the compound represented by the general formula (2-1) and / or the general formula (2-2) is, as a total amount, 0. 0 based on the total solid content of the actinic ray-sensitive or radiation-sensitive composition. 1-40 mass% is preferable, More preferably, it is 0.5-35 mass%, More preferably, it is 3-30 mass%.
Although the preferable specific example of a compound represented by general formula (2-1) and general formula (2-2) below is shown, this invention is not limited to these.

[Low molecular compound (1)]
The low molecular weight compound (1) of the present invention is a low molecular weight compound having a molecular weight of 500 to 5000 having an acid-decomposable group (G) that is decomposed by the action of an acid and promotes solubility in an alkaline developer, preferably In addition to the acid-decomposable group (G), it has a solubilizing group (S) that promotes solubility in a developer.

  Molecular weight becomes like this. Preferably it is 700-4000, More preferably, it is 1000-3000. If the molecular weight is less than 500, there is a concern that the resolution is deteriorated due to a limitation on the baking temperature of PB, PEB and the like. On the other hand, when the molecular weight exceeds 5000, the line edge roughness may deteriorate.

  The low molecular weight compound (1) of the present invention may be a so-called dendrimer or star polymer, but the compound having an unsaturated bond (so-called polymerizable monomer) is converted to an unsaturated bond using an initiator. It is not a so-called chain polymer obtained by cleaving and chain growing bonds.

The low molecular compound (1) of the present invention is not particularly limited in terms of structure as long as the above conditions are satisfied, but a preferred embodiment includes a compound represented by the following general formula (1-1).

In formula (1-1), W is an (a + b) -valent organic group, Y ₁ and Y ₂ are each independently a single bond or a divalent linking group, and G is decomposed by the action of an acid to form an alkali developer. An acid-decomposable group that promotes solubility, S is a solubilizing group that promotes solubility in an alkaline developer, and a and b each independently represent an integer of 1 to 30. When there are a plurality of groups in each parenthesis, the groups in the plurality of parentheses may be the same or different.

The organic group represented by W preferably has 1 to 300 carbon atoms, more preferably 10 to 200 carbon atoms.
a and b are preferably 2 to 20, and more preferably 3 to 10. The ratio of a to b (a / b) is preferably 1/10 to 10, more preferably 1/3 to 3, and further preferably 1/2 to 2.

The organic group represented by W preferably contains an aromatic ring. The aromatic ring may be monocyclic such as benzene ring and biphenyl ring, or two or more such as naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, torquesen ring The condensed ring which consists of these rings may be sufficient. These rings may contain a hetero atom. Examples of aromatic rings containing heteroatoms include furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, Isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxati An in ring, a phenothiazine ring, a phenazine ring, and the like.
The aromatic ring is preferably a benzene ring or a naphthalene ring.

Preferred examples of the organic group represented by W are shown below. In the following specific examples of the organic group represented by W, a bond bonded to Y ₁ or Y ₂ in General Formula (1-1) is present at an arbitrary position of *.

The divalent linking group represented by Y ₁ is _{preferably, * - Y 11 -, *} - Y 12 -, * - Y 12 -Y 11 -, * - Y 12 -C (= O) -Y 11 - , * −Y ₁₂ −C (= O) −, * −Y ₁₂ −SO ₂ −Y ₁₁ −, * −C (= O) −Y ₁₂ −Y ₁₁ −, * −SO ₂ −Y ₁₂ −Y _{11 -, * - Y 12 -C (} = O) -Y 12 '-Y 11 - and a combination thereof the arbitrarily. However, * represents a site that binds to W, Y ₁₁ is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, 6 to 20 carbon atoms A substituted or unsubstituted arylene group or a substituted or unsubstituted aralkylene group having 7 to 20 carbon atoms; Y ₁₂ and Y ₁₂ ′ each independently represent an oxygen atom, a sulfur atom or N (Ry); A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substitution having 7 to 20 carbon atoms Alternatively, it represents an unsubstituted aralkyl group.

The divalent linking group represented by Y ₂ is _{preferably, * - Y 21 -, *} - Y 22 -Y 21 -, * - Y 22 -C (= O) -Y 21 -, * - Y 22 - SO ₂ −Y ₂₁ −, * −C (= O) −Y ₂₂ −Y ₂₁ −, * −SO ₂ −Y ₂₂ −Y ₂₁ −, * −Y ₂₂ −C (= O) −Y ₂₂ '−Y _21- and any combination thereof. However, * represents a site that binds to W, Y ₂₁ is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, carbon atoms 6-20 A substituted or unsubstituted arylene group or a substituted or unsubstituted aralkylene group having 7 to 20 carbon atoms, Y ₂₂ and Y ₂₂ ′ each independently represents an oxygen atom, a sulfur atom or N (Ry); Is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a 7 to 20 carbon atom Represents a substituted or unsubstituted aralkyl group.

  Examples of the substituent that each of the above groups may have include, for example, a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), amino group, cyano group, hydroxyl group, alkoxy group (preferably carbon Number 1 to 15), a cycloalkyl group (preferably 3 to 15 carbon atoms), an aryl group (preferably 6 to 15 carbon atoms), an alkoxycarbonyl group (preferably 2 to 15 carbon atoms), an acyl group (preferably carbon 2-15) acylamino group (preferably 2-15 carbon atoms), carbamoyl group (preferably 1-15 carbon atoms), sulfonylamino group (preferably 2-15 carbon atoms), sulfamoyl group (preferably 1 carbon atom) To 15) and the like. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

[Acid-decomposable group (G) that is decomposed by the action of an acid to promote solubility in an alkali developer]
G represents an acid-decomposable group that is decomposed by the action of an acid and promotes solubility in an alkali developer. For example, an alkali-soluble group such as a carboxyl group or a hydroxyl group is protected with a group that is eliminated by the action of an acid. Preferred examples include acid-decomposable groups represented by the following general formulas (G11) and (G12).

In Formula (G11), R ₁₀₁ represents an alkyl group, R ₁₀₂ and R ₁₀₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and R ₁₀₂ and R ₁₀₃ are bonded to each other. A ring may be formed. However, R ₁₀₂ and R ₁₀₃ are not simultaneously hydrogen atoms. When either R ₁₀₂ or R ₁₀₃ is a hydrogen atom, the other is an aryl group.

The alkyl group of R _{101 to} R ₁₀₃ is preferably one having 1 to 20 carbon atoms, more preferably one having 1 to 10 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl. Particularly preferred are those having 1 to 4 carbon atoms such as a group, isobutyl group and t-butyl group.

The cycloalkyl group represented by R ₁₀₂ and R ₁₀₃ is preferably one having 3 to 20 carbon atoms, and may be monocyclic such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodeca A polycyclic group such as a nyl group, a tetracyclododecanyl group, and an adamantyl group may be used. The ring formed by combining R ₁₀₂ and R ₁₀₃ with each other preferably has 3 to 20 carbon atoms, and may be monocyclic such as a cyclopentyl group or a cyclohexyl group, or a norbornyl group. In addition, polycyclic ones such as a tetracyclodecanyl group and a tetracyclododecanyl group may be used. When R ₁₀₂ and R ₁₀₃ are bonded to each other to form a ring, R ₁₀₃ is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.

The aryl group represented by R ₁₀₂ and R _103, preferably has 6 to 20 carbon atoms, for example, a phenyl group, a naphthyl group, and the like.

In the formula (G12), R ₁₀₄ and R ₁₀₅ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, M represents a single bond or a divalent linking group, R ₁₀₆ represents an alkyl group, a cycloalkyl group, an alicyclic group which may contain a hetero atom, an aromatic ring group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group. .
q represents 0 or 1;
At least two of R ₁₀₄ , M, and R ₁₀₆ may combine to form a ring.
Note that q is 1 when both R ₁₀₄ and R ₁₀₅ are hydrogen atoms.

The alkyl group represented by R ₁₀₄ and R ₁₀₅ is preferably an alkyl group having 1 to 10 carbon atoms, specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group. Group, hexyl group, octyl group and the like.

The cycloalkyl group represented by R ₁₀₄ and R ₁₀₅ is preferably a cycloalkyl group having 3 to 15 carbon atoms, and specifically includes a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like. Can do.

The aryl group represented by R ₁₀₄ and R ₁₀₅ is preferably an aryl group having 6 to 15 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, a naphthyl group, and an anthryl group. .

The aralkyl group represented by R ₁₀₄ and R ₁₀₅ is preferably an aralkyl group having 6 to 20 carbon atoms, and specific examples include a benzyl group and a phenethyl group.

The divalent linking group represented by M is, for example, an alkylene group (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, etc.), cycloalkylene group (for example, cyclopentylene group, Cyclohexylene group), alkenylene group (for example, ethylene group, propenylene group, butenylene group, etc.), arylene group (for example, phenylene group, tolylene group, naphthylene group, etc.), -S-, -O-, -CO-, It is a divalent linking group in which —SO ₂ —, —N (R ₀ ) —, and a combination thereof. R ₀ represents a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group). Octyl group, etc.).
The alkyl group and cycloalkyl group represented by R ₁₀₆ have the same meanings as described for R ₁₀₄ and R ₁₀₅ above.

Examples of the alicyclic group and aromatic ring group in the alicyclic group optionally containing a heteroatom represented by R ₁₀₆ and the aromatic ring group optionally containing a heteroatom include R ₁₀₄ and R ₁₀₅ described above. Cycloalkyl group, aryl group, etc. are mentioned, Preferably it is C3-C15.

  Examples of the alicyclic group containing a hetero atom and the aromatic ring group containing a hetero atom include, for example, thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole. And groups having a heterocyclic structure such as pyrrolidone, but are not limited to these as long as the structure is generally called a heterocyclic ring (a ring formed of carbon and a heteroatom, or a ring formed of a heteroatom). .

As a ring that may be formed by combining at least two of R ₁₀₄ , M, and R ₁₀₆ , at least two of R ₁₀₄ , M, and R ₁₀₆ are combined to form, for example, a propylene group and a butylene group, Examples include forming a ring containing an oxygen atom, and a 5-membered or 6-membered ring is preferred.

The group represented by —M—R ₁₀₆ is preferably a group composed of 1 to 30 carbon atoms, more preferably a group composed of 5 to 20 carbon atoms.

When G is an acid-decomposable group represented by the formula (G12), W or Y ₁ directly bonded to G is preferably an aromatic group.

  Each of the above groups may have a substituent. Examples of the substituent include a nitro group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an amino group, a cyano group, a hydroxyl group, and an alkoxy group. (Preferably 1 to 15 carbon atoms), cycloalkyl group (preferably 3 to 15 carbon atoms), aryl group (preferably 6 to 15 carbon atoms), alkoxycarbonyl group (preferably 2 to 15 carbon atoms), acyl group (Preferably 2 to 15 carbon atoms) acylamino group (preferably 2 to 15 carbon atoms), carbamoyl group (preferably 1 to 15 carbon atoms), sulfonylamino group (preferably 2 to 15 carbon atoms), sulfamoyl group (preferably May include 1 to 15 carbon atoms. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

Specific examples of the groups represented by the general formulas (G11) and (G12) are shown below, but are not limited thereto. * Means a bond.

[Soluble auxiliary group (S) that promotes solubility in alkali developer]
As a solubilizing group that promotes the solubility of S in an alkaline developer, a group that is soluble in an alkaline developer, or a group that generates a group that is soluble in an alkaline developer by reaction with an alkaline developer. Can be mentioned.

Examples of the group having solubility in an alkali developer include a hydroxyl group, a carboxyl group, a sulfonamide group, a disulfonimide group, an acylsulfonylimide group, a diacylimide group, -C (OH) (Rf ₁ ) (Rf ₂ ) [Rf ₁ and Rf ₂ each independently represents a perfluoroalkyl group (preferably having 1 to 8 carbon atoms). ]. The presence form of a hydroxyl group as a group having solubility in an alkaline developer is preferably a hydroxyl group directly substituted with an aromatic ring, and more preferably a hydroxyl group directly substituted with a benzene ring or a naphthalene ring.

  A group having a lactone structure is preferable as the group that generates a group having solubility in an alkali developer by reaction with an alkali developer.

As the group having a lactone structure, any group having a lactone structure can be used, but a 5- to 7-membered ring lactone structure is preferable, and a bicyclo structure or a spiro structure is added to the 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed in the form to be formed are preferred. A group having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17) is more preferable. Among them, particularly preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14).

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

The group having a lactone group usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more.
Although the specific example of a lactone group is shown below, this invention is not limited to this.

Although the preferable specific example of a compound represented by general formula (1-1) below is given, this invention is not limited to these.

〔solvent〕
The solvent contained in the actinic ray-sensitive or radiation-sensitive composition of the present invention is preferably an organic solvent, and examples thereof include the following.

  Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate (PGMEA; 1-methoxy-2-acetoxypropane), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, Preferred is ethylene glycol monoethyl ether acetate.

  Examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether (PGME; 1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol Preferred is monoethyl ether.

Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
Preferred examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.

  Examples of the cyclic lactone include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-octano. Preferred are iclactone and α-hydroxy-γ-butyrolactone.

  Examples of the monoketone compound which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2 -Methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one, -Penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methyl Cyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methylcyclo A preferred example is heptanone.

Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
Preferred examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, and 1-methoxy-2-propyl acetate.
Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

Preferred solvents that can be used include 2-heptanone, cyclopentanone, γ-butyrolactone, cyclohexanone, butyl acetate, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 3-ethoxypropionic acid Examples include ethyl, ethyl pyruvate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, and propylene carbonate. From the viewpoint of reducing outgas, 2-heptanone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl Particularly preferred is a solvent having a boiling point of 150 ° C. or lower at normal pressure, such as ether. These solvents may be used alone or in combination of two or more.
The content of the solvent in the total amount of the composition of the present invention can be appropriately adjusted according to the desired film thickness, etc., but generally the total solid content concentration of the composition is preferably 0.5 to 30% by mass, preferably Is prepared to be 1.0 to 20% by mass, more preferably 1.5 to 10% by mass.

  The actinic ray-sensitive or radiation-sensitive composition of the present invention is further decomposed by the action of a basic compound and an acid, if necessary, in addition to the low molecular compound (1) and the acid generator (2) described above. Resins that increase the dissolution rate in alkaline water solubility, conventional photoacid generators, surfactants, acid-decomposable dissolution-inhibiting compounds, dyes, plasticizers, photosensitizers, and developer-promoting compounds for developers , A compound having a proton acceptor functional group and the like can be contained. At this time, the total content of the low molecular weight compound (1) and the acid generator (2) is 100% by mass of components other than the solvent contained in the actinic ray-sensitive or radiation-sensitive composition. It is preferably 80% by mass to 100% by mass, and more preferably 90% by mass to 100% by mass. When the content of the low molecular compound (1) is less than 60% by mass, the effect of the present invention cannot be sufficiently obtained, and the line edge roughness may be deteriorated.

[Other ingredients]
<Basic compound>
The actinic ray-sensitive or radiation-sensitive composition of the present invention preferably contains a basic compound.
The basic compound is preferably a nitrogen-containing organic basic compound.

  Although the compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(4) is used preferably.

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

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

  Specific examples of the compound of the general formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexylmethylamine, Tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N, N- Examples include dihexylaniline, 2,6-diisopropylaniline, 2,4,6-tri (t-butyl) aniline.

  In addition, a compound in which at least one R in the general formula (BS-1) is an alkyl group substituted with a hydroxyl group can be mentioned as one of preferable embodiments. Specific examples of the compound include triethanolamine and N, N-dihydroxyethylaniline.

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

(2) Compound having a nitrogen-containing heterocyclic structure The heterocyclic structure may or may not have aromaticity. Moreover, you may have two or more nitrogen atoms, Furthermore, you may contain hetero atoms other than nitrogen. Specifically, a compound having an imidazole structure (such as 2-phenylbenzimidazole), a compound having a piperidine structure (such as N-hydroxyethylpiperidine), a compound having a pyridine structure (such as 4-dimethylaminopyridine), an antipyrine structure Compounds having antipyrine and the like.

  A compound having two or more ring structures is also preferably used. Specific examples include 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] -undec-7-ene.

(3) Amine compound having a phenoxy group An amine compound having a phenoxy group has a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound. Preferably, it is a compound having at least one oxyalkylene chain between the phenoxy group and the nitrogen atom. The number of oxyalkylene chains in one molecule is preferably 3-9, more preferably 4-6. Among the oxyalkylene chains, —CH ₂ CH ₂ O— is preferable.

  Specific examples include 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine and US Patent Application Publication No. 2007/0224539. The compounds (C1-1) to (C3-3) exemplified in paragraph [0066] of the above.

(4) Ammonium salt Ammonium salts are also used as appropriate. Preferred is hydroxide or carboxylate. More specifically, tetraalkylammonium hydroxide represented by tetrabutylammonium hydroxide is preferable.

  In addition, compounds synthesized in Examples of JP-A No. 2002-363146, compounds described in paragraph 0108 of JP-A No. 2007-298869, and the like can also be used.

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

<Resin that is decomposed by the action of acid to increase the dissolution rate with respect to alkaline water solubility>
The actinic ray-sensitive or radiation-sensitive composition of the present invention may contain, in addition to the low molecular compound (1), a resin that decomposes by the action of an acid and increases the dissolution rate with respect to alkali water solubility.

  Resins that decompose due to the action of an acid and increase the dissolution rate in an alkaline aqueous solution (hereinafter also referred to as “acid-decomposable resins”) are not included in the main chain or side chain of the resin, It is a resin having a group (acid-decomposable group) that decomposes by the action of and produces an alkali-soluble group. Among these, a resin having an acid-decomposable group in the side chain is more preferable.

  The acid-decomposable resin is decomposed with an acid into an alkali-soluble resin as disclosed in European Patent No. 254853, JP-A-2-25850, JP-A-3-223860, JP-A-4-251259, and the like. It is possible to obtain an alkali-soluble resin monomer having a group capable of being decomposed or reacting with an acid-decomposable group by copolymerization with various monomers.

As the acid-decomposable group, for example, in a resin having an alkali-soluble group such as —COOH group and —OH group, a group in which the hydrogen atom of the alkali-soluble group shown on the left is substituted with a group capable of leaving by the action of an acid is preferable.
Specific examples of the acid-decomposable group include the same groups as the acid-decomposable groups described for the G component in the low molecular compound (1) of the present invention described above.

The resin having an alkali-soluble group is not particularly limited. For example, poly (o-hydroxystyrene), poly (m-hydroxystyrene), poly (p-hydroxystyrene) and copolymers thereof, hydrogenated poly (Hydroxystyrene), poly (hydroxystyrene) s having a substituent represented by the following structure, and resins having a phenolic hydroxyl group, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, hydrogen An alkali-soluble resin having a hydroxystyrene structural unit such as a modified novolak resin, and an alkali-soluble resin containing a repeating unit having a carboxyl group such as (meth) acrylic acid or norbornenecarboxylic acid.

The alkali dissolution rate of these alkali-soluble resins is preferably at least 170 kg / second as measured with 2.38 mass% tetramethylammonium hydroxide (TMAH) (23 ° C.). Particularly preferably, it is 330 Å / second or more.
The content of the group capable of decomposing with an acid is determined by the number of repeating units (X) having a group decomposable with an acid in the resin and the number of repeating units having an alkali-soluble group not protected by a group capable of leaving with an acid ( Y) and represented by X / (X + Y). The content is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, and still more preferably 0.05 to 0.40.

The weight average molecular weight of the acid-decomposable resin is preferably 50,000 or less, more preferably 1,000 to 20,000, and particularly preferably 1,000 to 10,000 as a polystyrene conversion value by the GPC method.
The dispersity (Mw / Mn) of the acid-decomposable resin is preferably 1.0 to 3.0, more preferably 1.05 to 2.0, and still more preferably 1.1 to 1.7.
Two or more acid-decomposable resins may be used in combination.
In the actinic ray-sensitive or radiation-sensitive composition of the present invention, the blending amount of the resin in the composition is preferably 0 to 20% by mass, more preferably 0 to 10% by mass in the total solid content of the composition. .

<Acid generator>
In the actinic ray-sensitive or radiation-sensitive composition of the present invention, an acid generator other than the acid generator (2) described above, that is, a compound that generates an acid having a volume of less than 305 ³ by irradiation with an actinic ray or radiation. (Hereinafter also referred to as “acid generator”).

  Examples of such an acid generator include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, or an actinic ray or radiation used for a microresist. A known compound that generates an acid by irradiation and a mixture thereof can be appropriately selected and used.

  Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates. Specific examples thereof include those described in [0164] to [0248] of US Patent Application Publication No. 2008 / 0241737A1. These acid generators may be used in combination of two or more.

  In the actinic ray-sensitive or radiation-sensitive composition of the present invention, when an acid generator is used in addition to the compound (2) having a photoacid generating structure, the acid generator is used alone or in combination of two or more. Can be used in combination. The content of the acid generator other than the compound (2) in the composition is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, based on the total solid content of the composition. The acid generator other than the compound (2) is not an essential component in the present invention, but is usually used in an amount of 0.01% by mass or more in order to obtain the effect of addition.

<Surfactant>
The actinic ray-sensitive or radiation-sensitive composition of the present invention preferably further contains a surfactant. As the surfactant, fluorine-based and / or silicon-based surfactants are preferable.
Surfactants corresponding to these include Megafac F176, Megafac R08 manufactured by Dainippon Ink and Chemicals, PF656, PF6320 manufactured by OMNOVA, Troisol S-366 manufactured by Troy Chemical, Sumitomo 3M Examples include Fluorad FC430 manufactured by Co., Ltd., polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

  Further, other surfactants other than fluorine-based and / or silicon-based surfactants can also be used. More specific examples include polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.

In addition, known surfactants can be used as appropriate. Examples of the surfactant that can be used include those described in [0273] et seq. Of US Patent Application Publication No. 2008/0248425.
Surfactants may be used alone or in combination of two or more.
The amount of the surfactant used is preferably 0 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total solid content of the actinic ray-sensitive or radiation-sensitive composition.

<Acid-decomposable dissolution inhibiting compound>
The actinic ray-sensitive or radiation-sensitive composition of the present invention is a dissolution inhibiting compound having a molecular weight of 3000 or less (hereinafter referred to as “dissolution inhibiting compound”) that decomposes by the action of an acid and increases the dissolution rate in an alkaline developer. Say).

  The dissolution inhibiting compound is preferably an alicyclic or aliphatic compound containing an acid-decomposable group such as a cholic acid derivative containing an acid-decomposable group described in Proceeding of SPIE, 2724, 355 (1996). . Examples of the acid-decomposable group and alicyclic structure are the same as those described for the acid-decomposable resin.

When the actinic ray-sensitive or radiation-sensitive composition of the present invention is irradiated with an electron beam or EUV light, it preferably contains a structure in which the phenolic hydroxyl group of the phenol compound is substituted with an acid-decomposable group. As a phenol compound, what contains 1-9 phenol frame | skeleton is preferable, More preferably, it contains 2-6 pieces.
The molecular weight of the dissolution inhibiting compound in the present invention is 3000 or less, preferably 300 to 3000, and more preferably 500 to 2500.

<Dye>
Suitable dyes include oily dyes and basic dyes.
<Photosensitizer>
In order to improve the acid generation efficiency by exposure, a photosensitizer can be added.
The dissolution accelerating compound for the developer that can be used in the present invention is a low molecular weight compound having a molecular weight of 1,000 or less and having two or more phenolic OH groups or one or more carboxy groups. When it has a carboxy group, an alicyclic or aliphatic compound is preferable. Examples of such a phenol compound having a molecular weight of 1000 or less include those described in JP-A-4-122938, JP-A-2-28531, U.S. Pat. No. 4,916,210, and European Patent 219294.
In addition, compounds having a proton acceptor functional group described in JP-A No. 2006-208781 and JP-A No. 2007-286574 can be suitably used for the composition of the present application.

<Pattern formation method>
The actinic ray-sensitive or radiation-sensitive composition of the present invention is coated on a support such as a substrate to form a film. The film thickness is preferably 0.02 to 0.1 μm.
As a method of coating on the substrate, spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.

For example, an actinic ray-sensitive or radiation-sensitive composition is coated on a substrate such as used in the manufacture of precision integrated circuit elements by a suitable coating method such as a spinner or a coater, and dried to form a film. In addition, a known antireflection film can be applied in advance. The substrate is not particularly limited, such as a quartz substrate having a Si, Si / SiO ₂ , SiN, TiN, or Cr layer.
The film is irradiated with an electron beam (EB), X-rays or EUV light through a mask as necessary, and is preferably baked (heated) and developed. Thereby, a good pattern can be obtained.

  In addition, when applying the composition of the present invention to the production of an information recording medium (more specifically, the production of a mold structure and a stamper used for the production of an information recording medium) described in the background art, the substrate is rotated. In other words, exposure / drawing can be performed by controlling the substrate in the r-θ direction. For details of this method and the manufacture of the mold structure by this method, refer to, for example, Japanese Patent No. 4109085 and Japanese Patent Application Laid-Open No. 2008-162101.

  In the development step, an alkaline developer is used as follows. Examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, di- Secondary amines such as n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium such as tetramethylammonium hydroxide and tetraethylammonium hydroxide Alkaline aqueous solutions such as salts, cyclic amines such as pyrrole and pihelidine can be used.

Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline developer.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.
An etching process, ion implantation, and the like are performed using the pattern formed as described above as a mask, and a semiconductor microcircuit, an imprint mold structure, and the like are created.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, the content of this invention is not limited by this.
Synthesis Example 1 Synthesis of Low Molecular Compound (B-6) A low molecular compound (B-6) was synthesized by the following route.

A mixture of Compound 1 (5.4 g), Compound 2 (5.2 g), potassium carbonate (3.45 g) and dimethylacetamide (100 ml) was stirred at 90 ° C. for 3 hours. The reaction solution was cooled to room temperature, poured into ethyl acetate (300 ml) / 1N aqueous hydrochloric acid (300 ml), and separated. The organic layer was washed with water (300 ml × 2 times) and saturated brine (300 ml), and then dried over sodium sulfate. After concentrating the solvent under reduced pressure, the residue was purified by a silica gel column to obtain compound (B-6) (2.2 g).

Synthesis Example 2 Synthesis of Low Molecular Compound (B-7) A low molecular compound (B-7) was synthesized by the following route.

Diisopropylamine (2.0 g) was added dropwise at 0 ° C. to a solution of compound 1 (5.4 g) in acetonitrile (50 ml), and further acetyl chloride (1.57 g) was added dropwise. The reaction solution was stirred at room temperature for 1 hour, poured into ethyl acetate (300 ml) / 1N aqueous hydrochloric acid (300 ml), and separated. The organic layer was washed with water (300 ml × 2 times) and saturated brine (300 ml), and then dried over sodium sulfate. The solvent was concentrated under reduced pressure and then recrystallized from ethyl acetate / hexane to obtain Compound 3 (3.2 g).

A solution containing compound 5 was obtained by stirring a solution of compound 3 (3.2 g), compound 4 (2.6 g) and camphorsulfonic acid (0.2 g) in ethyl acetate (50 ml) at room temperature for 5 hours. . A 28% sodium methoxide methanol solution (2.5 g) was added to the reaction solution, and the mixture was stirred at 40 ° C. for 3 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature and then slowly poured into water (200 ml) / ethyl acetate (200 ml) for extraction. The organic layer was washed with water (200 ml × 2 times) and saturated brine (200 ml), and then dried over sodium sulfate. The solvent was concentrated under reduced pressure, and then purified by a silica gel column to obtain compound (B-7) (2.1 g).

Synthesis Example 3 Synthesis of Low Molecular Compound (B-13) A low molecular compound (B-13) was synthesized by the following route.

A mixed solution of compound 6 (7.15 g), compound 7 (47.6 g) and potassium carbonate (16.6 g) in dimethylacetamide was stirred at 30 ° C. for 48 hours. The reaction solution was poured into ethyl acetate (1 L) / water (1 L) and separated. The organic layer was washed with water (500 ml × 2 times) and saturated brine (500 ml), and then dried over sodium sulfate. The solvent was concentrated under reduced pressure, and then purified with a silica gel column to obtain Compound 8 (9.6 g).

To a solution of compound 8 (9.6 g) in ethyl acetate (500 ml) was added 28% sodium methoxide methanol solution (10 g), and the mixture was stirred at 40 ° C. for 3 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature and then slowly poured into water (500 ml) / ethyl acetate (500 ml) for extraction. The organic layer was washed with water (500 ml × 2 times) and saturated brine (200 ml), and then dried over sodium sulfate. The solvent was concentrated under reduced pressure, and then purified by a silica gel column to obtain compound (B-13) (2.65 g).

Synthesis Example 4 Synthesis of Low Molecular Compound (B-14) A low molecular compound (B-14) was synthesized by the following route.

A mixed solution of Compound 6 (7.15 g), Compound 9 (55.7 g) and potassium carbonate (16.6 g) in dimethylacetamide was stirred at 30 ° C. for 48 hours. The reaction solution was poured into ethyl acetate (1 L) / water (1 L) and separated. The organic layer was washed with water (500 ml × 2 times) and saturated brine (500 ml), and then dried over sodium sulfate. The solvent was concentrated under reduced pressure, and then purified by a silica gel column to obtain Compound 10 (11.2 g).

To a solution of compound 10 (11.2 g) in ethyl acetate (500 ml) was added 28% sodium methoxide methanol solution (10 g), and the mixture was stirred at 40 ° C. for 3 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature and then slowly poured into water (500 ml) / ethyl acetate (500 ml) for extraction. The organic layer was washed with water (500 ml × 2 times) and saturated brine (200 ml), and then dried over sodium sulfate. After concentrating the solvent under reduced pressure, the residue was purified by a silica gel column to obtain compound (B-14) (4.1 g).

Synthesis Example 5 Synthesis of Low Molecular Compound (B-16) A low molecular compound (B-16) was synthesized by the following route.

Triethylamine (1.2 g) was added dropwise at 0 ° C. to a solution of compound 11 (5.0 g) and compound 12 (3.3 g) in tetrahydrofuran (30 ml), and the mixture was stirred at room temperature for 24 hours. The reaction mixture was slowly poured into 1N aqueous hydrochloric acid (300 ml) / ethyl acetate (300 ml) and extracted. The organic layer was washed with water (300 ml × 2 times) and saturated brine (300 ml), and then dried over sodium sulfate. After concentrating the solvent under reduced pressure, the residue was purified by a silica gel column to obtain compound (B-16) (3.8 g).

Synthesis Example 6 Synthesis of Low Molecular Compound (B-18) Low molecular compound C was synthesized by the following route.

To a solution of compound 13 (9.0 g) and resorcinol (3.0 g) in ethanol (200 ml) was added aqueous hydrochloric acid (10 ml), and the mixture was stirred at room temperature for 75 hours. The produced crystals were filtered, washed with water, dried and then purified through a silica gel column to give compound (B-18).

Synthesis Example 7 Synthesis of Low Molecular Compound (B-19) A low molecular compound (B-19) was synthesized by the following route.

A mixture of compound 14 (3.5 g), di-t-butyl dicarbonate (17.4 ml), 18-crown-6 (15.1 g) and potassium carbonate (10 g) in tetrahydrofuran (180 ml) was placed under an argon atmosphere. The mixture was stirred at 40 ° C. for 1 hour and 30 minutes. The reaction mixture was poured into ethyl acetate (500 ml) / water (500 ml) and extracted. The organic layer was washed with dilute aqueous hydrochloric acid (300 ml), aqueous sodium bicarbonate (300 ml), water (300 ml) and saturated brine (300 ml), and dried over sodium sulfate. The solvent was concentrated under reduced pressure, and then purified by a silica gel column to obtain compound (B-19).

Synthesis Example 8 Synthesis of Low Molecular Compound (B-31) A low molecular compound (B-31) was synthesized by the following route.

Synthesis of Compound 16 Hexabromobenzene (1.0 g), Compound 15 (8.9 g), palladium (II) chloride bisacetonitryl complex (0.52 g), triphenylphosphine (2.62 g), cuprous chloride (0.76 g) and triethylamine (100 ml) were stirred at reflux temperature for 6 hours under a nitrogen atmosphere.
The reaction solution was cooled to room temperature and then slowly poured into 1N aqueous hydrochloric acid (300 ml) / ethyl acetate (300 ml) for extraction. The organic layer was washed with water (300 ml × 2 times) and saturated brine (300 ml), and then dried over sodium sulfate. After concentrating the solvent under reduced pressure, the residue was purified by a silica gel column to obtain Compound 16 (1.72 g).

Synthesis of Compound (B-31) A solution of Compound 16 (1.72 g) and 0.5 mass% palladium carbon (0.15 g) in ethyl acetate (60 ml) / methanol (60 ml) was subjected to hydrogen pressure (5.0 MPa). The mixture was stirred at 50 ° C. for 4 hours. After cooling the reaction solution to room temperature, the catalyst was filtered off. The filtrate was concentrated under reduced pressure and purified by a silica gel column to obtain compound (B-31) (0.73 g, 0.33 mmol).

  The low molecular weight compounds (B-25) and (B-26) were synthesized by the same method as the above compound (B-31).

Synthesis Example 9 Synthesis of Acid Generator (A-1) Aluminum chloride (20.5 g) was added to benzene (60.0 g), and the mixture was cooled and stirred at 3 ° C., and cyclohexyl chloride (121.2 g) was slowly added dropwise. After dropping, the mixture was stirred at room temperature for 5 hours and poured into ice water. The organic layer was extracted with ethyl acetate, and the obtained organic layer was distilled off under reduced pressure at 40 ° C. Furthermore, after depressurizingly distilling at 170 degreeC, it cooled to room temperature, thrown in acetone (150 ml), and recrystallized. The precipitated crystals were collected by filtration to obtain 2,4,6-tricyclohexylbromobenzene (42 g).

  2,4,6-Tricyclohexylbromobenzene (30 g) was dissolved in methylene chloride (50 ml), cooled and stirred at 3 ° C., and chlorosulfonic acid (15.2 g) was slowly added dropwise. After dropping, the mixture was stirred at room temperature for 5 hours, ice (10 g) was added, and then 50% aqueous sodium hydroxide solution (40 g) was added. Ethanol (20 g) was further added, and the mixture was stirred at 50 ° C. for 1 hr. Insoluble matters were removed by filtration, and the residue was distilled off under reduced pressure at 40 ° C. The precipitated crystals were collected by filtration and washed with hexane to obtain sodium 1,3,5-tricyclohexylbenzenesulfonate (30 g).

  Triphenylsulfonium bromide (4.0 g) was dissolved in methanol (20 ml), and sodium 1,3,5-tricyclohexylbenzenesulfonate (5.0 g) dissolved in 20 ml of methanol was added. After stirring at room temperature for 2 hours, ion-exchanged water (50 ml) was added and extracted with chloroform. The obtained organic layer was washed with water and distilled off under reduced pressure at 40 ° C., and the resulting crystal was recrystallized with a methanol / ethyl acetate solvent to obtain an acid generator (A-1) (5.0 g). It was.

Synthesis Example 10 Synthesis of acid generator (A-20)
2,4,6-Tricyclohexylbromobenzene (20.0 g) was dissolved in diethyl ether (800 ml), and tetramethylethylenediamine (6.0 g) and n-butyllithium (1.63 M hexane solution) (under a nitrogen atmosphere) 31.9 ml) was added at 0 ° C. After stirring at 0 ° C. for 1 hour, the reaction solution was added to a solution of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyldifluoride (15.7 g) in diethyl ether (200 ml). The solution was added dropwise at 0 ° C. over 30 minutes. After dropping, the mixture was further stirred for 30 minutes, distilled water (200 ml) was added, and the organic layer was washed twice with saturated brine. The solvent was removed, methanol (100 ml) and 1N aqueous sodium hydroxide solution (100 ml) were added, and the mixture was stirred for 1 hour. After the methanol was distilled off, ethyl acetate was added and the organic layer was washed twice with saturated brine. The solvent was distilled off, the obtained solid was washed with hexane, the obtained solid was dissolved in methanol (100 ml), triphenylsulfonium bromide (10 g) was added, and the mixture was stirred for 2 hours. After the solvent was distilled off, ethyl acetate was added, the organic layer was washed successively with a saturated aqueous sodium hydrogen carbonate solution and water, and the solvent was removed to obtain an acid generator (A-20) (23.5 g). .
For the acid generators (A-3), (A-9), (A-13), (A-14), (A-17), and (A-23), the same method as the above synthesis method is used. And synthesized.

Synthesis of Comparative Compound: Synthesis of Polymer Compound (P-1) 1-Methoxy-2-propanol (50 ml) was heated to 80 ° C. under a nitrogen stream. While stirring this solution, p-hydroxystyrene (7.2 g, 60 mmol), 1-methyl-1-adamantyl methacrylate (9.4 g, 40 mmol), dimethyl 2,2′-azobisisolacrate (V-601, Wako Pure) A mixed solution of 0.8 g (3.5 mmol) manufactured by Yakuhin Kogyo Co., Ltd. and 1-methoxy-2-propanol (50 ml) was added dropwise over 5 hours. After completion of dropping, the mixture was further stirred at 80 ° C. for 3 hours. The reaction solution was allowed to cool and then reprecipitated with a large amount of hexane / ethyl acetate and vacuum dried to obtain Comparative Resin P-1 (12.3 g). When ¹ H NMR of the obtained resin was measured, the composition ratio of the resin (65/35 molar ratio as the order from the left of the repeating unit in the above structural formula) was calculated. Moreover, the weight average molecular weight (Mw: polystyrene conversion) calculated | required from GPC (carrier: N-methyl-2-pyrrolidone (NMP)) was Mw = 4800 and Mw / Mn = 1.56.
The polymer compound (P-2) was also synthesized using a method similar to the method for synthesizing the polymer compound (P-1).

Examples 1-12 and Comparative Examples 1-13
<Evaluation (EB)>
The components shown in Table 1 below were dissolved in the solvents shown in Table 1 to prepare a solution having a total solid content concentration of 5.0% by mass. This solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm to obtain an actinic ray-sensitive or radiation-sensitive composition (positive resist solution). The prepared positive resist solution is uniformly coated on a hexamethyldisilazane-treated silicon substrate using a spin coater, and heated and dried on a hot plate at 110 ° C. for 90 seconds to obtain a resist having a film thickness of 60 nm. A film was formed.

  This resist film was irradiated with an electron beam using an electron beam irradiation apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage: 50 keV). Immediately after the irradiation, it was heated on a hot plate at 120 ° C. for 90 seconds. Furthermore, development was performed at 23 ° C. for 60 seconds using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass, rinsed with pure water for 30 seconds, and then dried to form a line and space pattern. Was evaluated by the following method. The evaluation results are shown in the same table.

〔sensitivity〕
The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.). Sensitivity was defined as the minimum irradiation energy when resolving a 100 nm line (line: space = 1: 1).

[Resolution]
The resolving power was defined as the limiting resolving power (minimum line width at which lines and spaces were separated and resolved) at the irradiation dose showing the above sensitivity.

[Line edge roughness (LER)]
The distance from the reference line where there should be an edge, using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.) for any 30 points in the length direction 50 μm of the 100 nm line pattern at the irradiation amount showing the sensitivity described above. Was measured, the standard deviation was obtained, and 3σ was calculated.

[Pattern shape]
The cross-sectional shape of the 100 nm line pattern at the irradiation dose showing the above sensitivity was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.), and three-step evaluation was performed: rectangular, slightly tapered, and tapered.

[Dry etching resistance]
A resist film with a film thickness of 60 nm was prepared in the same manner as described above, and was dried for 2 minutes with a gas of Ar / C ₄ F ₉ / O ₂ = 100: 4: 2 using a dry etcher (U-621) manufactured by Hitachi High Technology. Dry etching was performed, and the etching rate per second was calculated from the measurement of the remaining film amount.

The structures of the polymer compound, basic compound, and photoacid generator used in Examples and Comparative Examples are shown below.

  Surfactants and solvents used in Examples and Comparative Examples are shown below.

[Surfactant]
W-1: Megafac F176 (Dainippon Ink Chemical Co., Ltd., fluorine-based)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd., fluorine and silicon)
W-3: Polysiloxane polymer (Shin-Etsu Chemical Co., Ltd., silicon-based)
〔solvent〕
S1: Propylene glycol monomethyl ether acetate (PGMEA)
S2: Propylene glycol monomethyl ether (PGME)
S3: Ethyl lactate S4: Cyclohexanone The results shown in Table 1, in particular, Example 1 and Comparative Examples 1, 2, 3, Example 2, Comparative Example 4, 5, Example 3, Comparative Example 6, and Example 4 Example 7, Example 5 and Comparative Example 8, Example 6 and Comparative Example 9, Example 7 and Comparative Example 10, Example 8 and Comparative Example 11, Example 9 and Comparative Example 12, Examples 10, 11, 12 From Comparative Example 13, the actinic ray-sensitive or radiation-sensitive composition of the present invention simultaneously satisfies high sensitivity, high resolution, good pattern shape, good line edge roughness, and good dry etching resistance. Is clear.

Claims (13)

Low molecular compound (1) having a molecular weight of 500 to 5000 having an acid decomposable group (G) that is decomposed by the action of an acid to promote solubility in an alkali developer (excluding a chain polymer), and An actinic ray-sensitive material represented by the general formula (2-1) or (2-3), which contains a compound (2) that generates an acid having a volume of 305 to ³ or more upon irradiation with an actinic ray or radiation. Radiation sensitive composition.

In general formula (2-1),
Ar represents an aromatic ring, and may further have a substituent in addition to the — (AB) group.
n represents an integer of 1 or more, A represents a single bond or a divalent linking group, and B represents a group having a cyclic aliphatic group having 4 or more carbon atoms.
When n is 2 or more, a plurality of — (AB) groups may be the same or different.
Q ⁻ represents an anion having a pKa of a conjugate acid of 6 or less, and M ⁺ represents an organic onium ion.
In general formula (2-3),
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
J represents a single bond or a linear, branched or cyclic alkylene group which may contain ether oxygen, an arylene group, or a group consisting of a combination of these groups, and the group to be combined is an oxygen atom. May be connected.
L is, -COO -, - OCO- and -SO ₂ - represents a divalent linking group selected pressurized et al. When there are a plurality of L, they may be the same or different.
Ar represents a benzene ring, a naphthalene ring or an anthracene ring, and may further have a substituent in addition to the — ( AB ) group.
n represents an integer of 1 or more, A represents a single bond or a divalent linking group, and B represents a group having a cyclic aliphatic group having 4 or more carbon atoms.
When n is 2 or more, a plurality of — (AB) groups may be the same or different.
x represents an integer of 1 to 20, and y represents an integer of 0 to 10.
Q ⁻ represents an anion having a pKa of a conjugate acid of 6 or less, and M ⁺ represents an organic onium ion.   The actinic-ray sensitive or radiation sensitive composition of Claim 1 whose molecular weight of a low molecular compound (1) is 1000-3000. L in the general formula (2-3) is a divalent linking group selected from —COO—, —OCO—, —CO—, —O—, —S—, —SO— and —SO ₂ —. The actinic ray-sensitive or radiation-sensitive composition according to claim 1 or 2.   The actinic ray-sensitive or radiation-sensitive property according to any one of claims 1 to 3, wherein A in the general formula (2-1) and A in the general formula (2-3) are single bonds. Composition.   The actinic ray-sensitive property according to any one of claims 1 to 4, wherein n in the general formula (2-1) and n in the general formula (2-3) are integers of 2 to 5. Radiation sensitive composition.   The actinic ray-sensitive or radiation-sensitive composition according to any one of claims 1 to 4, wherein n in the general formula (2-1) and n in the general formula (2-3) are 3. object.   The actinic ray-sensitive or radiation-sensitive property according to any one of claims 1 to 6, wherein B in the general formula (2-1) and B in the general formula (2-3) are cyclohexyl groups. Composition.   The actinic ray-sensitive or radiation-sensitive composition according to any one of claims 1 to 7, wherein the compound (2) is a compound represented by the general formula (2-1). Q in the general formula (2-1) in ^-, and, Q in the general formula (2-3) ^- is a sulfonic acid anion, ray- according to any one of claims 1-8 or Radiation sensitive composition.   The actinic ray according to any one of claims 1 to 9, wherein the low molecular compound (1) further has a solubilizing group (S) that promotes solubility in an alkaline developer. Or radiation sensitive compositions. The actinic ray-sensitive or radiation-sensitive composition according to any one of claims 1 to 10, wherein the low molecular compound (1) is a compound represented by the following general formula (1-1). .

In formula (1-1), W is an (a + b) -valent organic group, Y ₁ and Y ₂ are each independently a single bond or a divalent linking group, and G is decomposed by the action of an acid to form an alkali developer. An acid-decomposable group that promotes solubility, S is a solubilizing group that promotes solubility in an alkaline developer, and a and b each independently represent an integer of 1 to 30. When there are a plurality of groups in each parenthesis, the groups in the plurality of parentheses may be the same or different.   A pattern forming method comprising forming a film using the actinic ray-sensitive or radiation-sensitive composition according to claim 1, and exposing and developing the film.   The pattern forming method according to claim 12, wherein the exposure is performed using X-rays, electron beams, or EUV.