JP2003295437A - Negative resist composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative resist composition having high sensitivity and high resolving power and reduced in development defects in pattern formation with an actinic radiation (electron beam, X-ray or EUV (extreme-ultraviolet ray)). <P>SOLUTION: In the negative resist composition comprising (A) an alkali- soluble resin, (B) a compound which generates an acid upon irradiation with an actinic radiation and (C) a crosslinking agent, the alkali-soluble resin is a graft polymer. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to actinic radiation (electron
X-ray, X-ray or EUV (Extreme Ultraviolet) irradiation
A negative resist composition for pattern formation
The [0002] 2. Description of the Related Art Integrated circuits are becoming more and more integrated.
In the manufacture of semiconductor substrates such as VLSI, half
Processing of ultra-fine patterns consisting of line widths smaller than Minklon
It has come to be needed. To meet that need
Use of irradiation equipment used for photolithography
Wavelengths have become shorter and now far UV and excimer
Zer light (XeCl, KrF, ArF, etc.) is considered
It is getting up. Furthermore, it can be further updated by electron beam or X-ray.
Recently, the formation of fine patterns has been studied. In particular, the electron beam or X-ray is the next generation or
Positioned as a next-generation pattern formation technology
The In electron beam lithography, an accelerated electron beam is registered.
Energy in the process of collision scattering with atoms constituting the strike material
That releases resist and sensitizes resist materials.
The Increased straightness by using highly accelerated electron beam
However, the influence of electron scattering is reduced and the rectangular shape is high resolution.
Pattern formation is possible, but on the other hand, electron beam transparency
Increases and sensitivity decreases. In this way, an electron beam
In lithography, sensitivity, resolution, and resist type
There is a trade-off relationship between the two
It was a challenge. Conventionally chemically amplified negative resists
Various alkali-soluble resins have been proposed. JP
No. 8-152717 was partially alkyl etherified
Polyvinylphenol is disclosed in JP-A-6-67431.
Kaihei 10-10733 has vinyl phenol and styrene.
No. 2505033 is a novolak copolymer.
Japanese Patent Laid-Open Nos. 7-31463 and 8-29.
No. 2559 has monodisperse polyvinylphenol
Although disclosed, these alkali-soluble resins
High level of sensitivity and resolution under sub-beam or X-ray irradiation
It was not something that could be compatible. In an electron beam resist, first, a binder is electrically charged.
The acid generator accepts secondary electrons generated from the strands.
It is reported that it decomposes and generates acid. by
Incorporate structures and forms that easily generate secondary electrons in the binder.
High acid generation efficiency, advantageous for electron beam resist
it is conceivable that. The same applies to EUV and X-ray resists.
It is reported that the acid generator is decomposed by secondary electrons and acid is generated.
Structure that easily generates secondary electrons in the binder,
Incorporating forms is considered to work effectively as well.
available. J. Vac. Sci. Technol., B (1998) 16 (6), 37
In 01, anti-static on the backbone of acrylic polymer for image formation
Graft polymer grafted with conductive polymer branches
Electron beam lithograph with negative resist material using
Describes technology to prevent pattern misalignment
The However, it is not possible to achieve both high sensitivity and high resolution.
It was enough. US5055379 has gelatin branch
Negative-type photo-restraint containing dye-containing fine particles grafted as
Jist is disclosed, but for electron beam or X-ray exposure
However, high sensitivity and high resolution are not compatible. Ma
Polymer (1990) and 31 (8) contain photocrosslinkable silicon.
Two-layer coating with improved cross-linking efficiency using grafted polymer
Dist system is described, but electron beam or X
To achieve both high sensitivity and high resolution in line exposure
It was insufficient. JP-A-2-103215 discloses alkyl
Group, halogen-substituted alkyl group, alkyl ether
Group or an acrylic group having a phenylalkyl group
Branched polymer or acrylic ester polymer
Active energy ray with graft polymer in part
Technology to improve support adhesion by curable resin composition
Although disclosed, it is high in electron beam or X-ray exposure.
It was insufficient to achieve both sensitivity and high resolution. More
In Indian J. Technol., (1976) 14 (9), 444, 4-
And maleic anhydride as a branch to 4'-glycidoxychalcone
Graft polymer grafted with acid / styrene alternating copolymer
UV cross-linked negative photoresist with limer is disclosed
However, it has high sensitivity in electron beam or X-ray exposure.
It was still insufficient to achieve both high resolution. Also,
Improve development defects with these compositions and processes
That was not enough. Also, a conventional resist group for electron beam and X-ray
The composition reduces development defects as well as high sensitivity and resolution.
It was difficult to do. [0008] The object of the present invention is to provide an activity.
Putter by radiation (electron beam, X-ray or EUV) irradiation
Reduces development defects with high sensitivity and resolution
It is an object of the present invention to provide a negative resist composition. [0009] That is, according to the present invention,
The above-mentioned object is achieved by the following negative resist composition.
The (1) (A) Alkali-soluble resin, (B)
A compound that generates an acid upon irradiation with actinic radiation, and
(C) In a negative resist composition containing a crosslinking agent
The alkali-soluble resin is a graft polymer.
A negative resist composition characterized by the above. The following are further preferred embodiments of the present invention.
Geru. (2) The alkali-soluble resin contains an alkali-soluble group
Having a repeating unit in the trunk of the graft polymer,
The branch is not a conductive polymer (1)
A negative resist composition as described in 1. above. (3) The alkali-soluble resin contains an alkali-soluble group
Having a repeating unit in the branch of the graft polymer
Negative resist composition as described in (1)
Stuff. (4) The alkali-soluble resin which is a graft polymer
Contains a structural unit represented by the following general formula (1)
The net according to any one of (1) to (3) above,
Ga type resist composition. [0012] [Chemical 1] Where R₁Is a hydrogen atom, halogen atom,
An ano group, an alkyl group or
Represents a loalkyl group. R₂Has a hydrogen atom and a substituent
Alkyl group, cycloalkyl group, aryl
Represents a group, an aralkyl group, or an acyl group. R_Three, R_Four
May be the same or different, hydrogen atom, halogen atom
Alkyl, cyano group, or substituent which may have a substituent
Group, cycloalkyl group, alkenyl group, aralkyl
Represents a group or an aryl group. A is a single bond, a substituent
An alkylene group, alkenylene group, cyclo
An alkylene group, an arylene group, -O-,-
SO₂-, -O-CO-R_Five-, -CO-O-R₆-,-
CO-N (R₇-R₈-Represents. R_Five, R₆, R₈Is the same
However, they may be different and may have a single bond or a substituent.
Alkylene group, alkenylene group, cycloalkylene group
Group, an arylene group alone, or these groups and
-Tel structure, ester structure, amide structure, urethane structure
Or at least one selected from the group of ureido structures
Represents a divalent group formed by combining species. R₇Is the same
However, they may be different and have a hydrogen atom or a substituent.
Alkyl group, cycloalkyl group, aralkyl
Represents a group or an aryl group. n represents an integer of 1 to 3.
Multiple R₂Or R₂And R_ThreeOr R_FourIs connected to the ring
May be formed. (5) Alkaline which is a graft polymer
Re-soluble resin satisfies the following conditions (a) and (b)
Any one of the above (1) to (3)
Negative resist composition. (A) an aromatic ring having 6 to 20 carbon atoms and
An ethylenically unsaturated group bonded via a contact or linking group
Less repeating units derived from monomers having
Have both. (B) π electrons of the aromatic ring and non-covalent electricity of substituents on the aromatic ring
The following relationship holds between the number of electrons in the child pair. [0015] [Expression 1] (Where Nπ represents the total number of π electrons, and N
_loneIs a straight chain having 1 to 12 carbon atoms as the substituent
, Branched or cyclic alkoxy groups, alkenyl
Oxy, aryloxy, aralkyloxy,
Or the total number of electrons in the lone pair of hydroxyl groups. 2 or more
The two adjacent alkoxy groups or hydroxyl groups are bonded to each other.
Together, they may form a ring structure of five or more members. ) (6) The alkali-soluble resin which is a graft polymer
Is a repeating unit represented by the following general formulas (3) to (7):
Having at least one of the positions as a constituent component
The negative resist composition as described in (5) above. [0017] [Chemical 2][0018] [Chemical 3]In the general formulas (3) to (7), R
₁₀₁Represents a hydrogen atom or a methyl group. L is bivalent
Represents a linking group. Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, Ri,
Rj, Rk and Rl are each independently a straight chain having 1 to 12 carbon atoms.
, Branched or cyclic alkyl groups, alkenyl
Group, aryl group, aralkyl group, or hydrogen atom
The In addition, these are connected to each other to form 5 having 24 or less carbon atoms.
You may form a ring more than a member. l, m, n, p, q, r, s, t, u, v, w,
x represents an integer from 0 to 3, l + m + n = 2,3, p + q + r = 0,1,
2,3, s + t + u = 0,1,2,3, v + w + x = 0,1,2,3. (7) The alkali-soluble resin which is a graft polymer
Is selected from the following group (1)
Negative resist composition in any one of-(3). (C) Partially alkyletherized polyhydroxystyrene
Graft polymer having len at the trunk and / or branch
-. (D) the hydroxystyrene / styrene copolymer is
And / or graph polymer at the branch. (E) Polyhydroxystyrene as the trunk, alkylate
Graph having styrene styrene and / or styrene at the branch
Topolymer. (F) Branch of polyhydroxystyrene, alkyl ether
Graph having styrene styrene and / or styrene in the trunk
Topolymer. (8) Graftmer has a weight average molecular weight of 2
000-500000, more preferably 3000-30
(1) to (7) above, which is 0000
The negative resist composition as described in any one of the above. (9) The compound of component (B) is sulfonium or iodine
Specially selected from donium sulfonate compounds
Negative type according to any one of (1) to (8) above
Resist composition. (10) The compound of component (B) is N-hydroxyimide
The sulfonic acid ester compound of
Negative resist group according to any one of (1) to (9)
Adult. (11) The component (C) contains 3 benzene ring atoms in the molecule.
~ 5, molecular weight is 1200 or less, hydroxy
Methyl group and / or alkoxymethyl group as its benzene
It must be a phenol derivative with two or more ring groups.
Any one of (1) to (10) above,
Negative resist composition. [0021] DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the negative resist set of the present invention.
The composition will be described. [1] (B) Acid is generated by irradiation with actinic radiation.
Generated compounds (hereinafter also referred to as acid generators) The acid generator used in the present invention is actinic radiation (electrical).
A compound that generates acid upon irradiation with a daughter beam, X-ray or EUV.
Any compound can be used as long as it is a product. So
As an acid generator, such as photoinitiation of photocationic polymerization
Agent, photoinitiator for radical photopolymerization, photodecolorant for dyes, light
Used for discoloring agents or microresists
Generates acid by irradiation with known electron beam, X-ray or EUV
Compounds and mixtures thereof are appropriately selected and used.
be able to. For example, diazonium salt, phosphonium
Salt, iodonium salt, sulfonium salt, selenonium
Salts, onium salts such as arsonium salts, organic halogen compounds
, Organometallic / organic halide, o-nitrobenzyl
For acid generators with type protecting groups, iminosulfonates, etc.
Representative compounds that generate sulfonic acid, disulfonation
Compound can be mentioned. It also generates these acids
Lead groups or compounds to the main or side chain of the polymer
Compounds, such as JP-A 63-26653,
JP 55-164824, JP 62-69263
JP, 63-146038, JP 63-163
452, JP-A-62-153853, JP-A-63-
146029 etc. can be used.
The In addition, US Pat. No. 3,779,778, European patent
Also used are compounds that generate acids as described in No. 126,712, etc.
Can be used. In the present invention, oni which generates an organic acid is used.
Umum salt compounds are preferred, particularly preferably the following general formula
(I) to an onium salt compound represented by the general formula (III)
is there. [0025] [Formula 4] [In the general formulas (I) to (III), R₁~ R
₃₇Is a hydrogen atom, alkyl group, alkoxyl group, hydro
Xyl group, halogen atom, or -SR₃₈The group that can be indicated by
Represent. -S-R₃₈R inside₃₈Is an alkyl group or aryl
Represents a group. R₁~ R₃₈May be the same or different
It may be. R₁~ R₁₅Is selected from
Two or more are bonded directly to each other at the end, or
Bonded through an element selected from elemental, sulfur and nitrogen
To form a ring structure. R₁₆~ R₂₇in the case of
In the same manner, a ring structure may be formed. R₂₈~ R
₃₇In this case, a ring structure may be formed in the same manner.
X^-Is an anion of sulfonic acid. ] R in general formula (I) to general formula (III)₁~ R
₃₇Is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group
Sil group, halogen atom, or -SR₃₈To show in
It is a group that can. R₁~ R₃₇The alkyl group represented by
Or may be branched or annular. Linear or minute
Examples of the branched alkyl group include a methyl group, ethyl
Group, propyl group, n-butyl group, sec-butyl group, t
-A butyl group, for example, an alkyl group having 1 to 4 carbon atoms
Can be mentioned. Examples of the cyclic alkyl group include
Cyclopropyl group, cyclopentyl group, cyclohexyl
And an alkyl group having 3 to 8 carbon atoms such as a group.
The R₁~ R₃₇The alkoxy group represented by
Further, it may be branched or a cyclic alkoxy group. Straight chain
Examples of the branched or branched alkoxy group include 1 to 1 carbon atoms.
8 things such as methoxy, ethoxy, hydroxy
Ethoxy group, propoxy group, n-butoxy group, isobut
Xyl group, sec-butoxy group, t-butoxy group, octy
Examples thereof include a ruoxy group. Cyclic alkoxy
Examples of the group include a cyclopentyloxy group and a cyclo
A hexyloxy group is mentioned. R₁~ R₃₇As the halogen atom represented by
List fluorine, chlorine, bromine, and iodine atoms
You can. R₁~ R₃₇-S-R represented by₃₈R inside₃₈Is
An alkyl group or an aryl group. R₃₈Alk
As the range of the ru group, for example, R₁~ R₃₇Alkyl represented by
Any of the alkyl groups already listed as groups
be able to. R₃₈The aryl group represented by is a phenyl group,
Carbon such as tolyl group, methoxyphenyl group, naphthyl group
A few 6-14 aryl groups can be mentioned. R₁
~ R₃₈The alkyl group represented by
It is possible to bond more substituents to part of the group to increase the number of carbon atoms.
Or may not have a substituent. Further join
The substituent which may be used preferably has 1 carbon atom.
-4 alkoxy groups, aryl having 6-10 carbon atoms
Group, alkenyl group having 2 to 6 carbon atoms.
Cyano, hydroxy, carboxy, alkoxy
A cicarbonyl group, a nitro group, etc. can also be mentioned. So
In addition, a halogen atom may be used. For example, fluorine atom,
A chlorine atom and an iodine atom can be mentioned. R in the general formula (I)₁~ R₁₅The group represented by
Two or more of them may combine to form a ring
Yes. The ring is R₁~ R₁₅The end of the group indicated by
You may make it. Select from carbon, oxygen, sulfur and nitrogen
Indirectly linked through one or more elements
Or a ring may be formed. R₁~ R₁₅2 of
Examples of the ring structure formed by combining the above include furan ring and di-
Hydrofuran ring, pyran ring, trihydropyran ring, thio
The same structure as the ring structure found in phen and pyrrole rings
You can mention construction. R in general formula (II) ₁₆~ R₂₇
The same can be said about. Two or more
It may be bonded directly or indirectly to form a ring. General
R in formula (III)₂₈~ R₃₇The same applies to. The general formulas (I) to (III) are represented by X^-Have one
X of general formulas (I) to (III)^-Is the sulfonic acid
Is on. The acid that forms the anion is alkyls
Sulfonic acid, benzenesulfonic acid, naphthalenesulfone
Acid or acid selected from anthracene sulfonic acid
It is preferable that The acid contains one or more fluorine atoms
More preferably. Or its acid is its fluorine
An alkyl group together with or in place of a fluorine atom,
Alkoxyl group, acyl group, acyloxyl group, sulfoni
Group, sulfonyloxy group, sulfonylamino group, ant
Group, aralkyl group, alkoxycarbonyl group,
Having at least one organic group selected from the group consisting of
Moreover, the organic group has at least one fluorine atom added.
Is preferably substituted. Also, the above alkyl
Sulfonic acid, benzene sulfonic acid, naphthalene sulfone
Acid or anthracene sulfonic acid is a halo other than fluorine.
May be substituted with a gen atom, hydroxyl group, nitro group, etc.
Yes. X^-Benzenesulfo to form anions
The alkyl group bonded to the acid or the like has, for example, 1 to 1 carbon atoms.
2 alkyl groups. The alkyl group may be linear
Further, it may be branched or annular. At least one
Fluorine atoms, preferably no more than 25 fluorine atoms are substituted
doing. Specifically, trifluoromethyl group, pentafluoro
Loethyl group, 2,2,2-trifluoroethyl group, hepta
Fluoropropyl group, heptafluoroisopropyl group, par
Fluorobutyl group, perfluorooctyl group, perfluorodo
List decyl group, perfluorocyclohexyl group, etc.
Can do. Among them, all carbon atoms substituted with fluorine are 1
~ 4 perfluoroalkyl groups are preferred. Alkyl group and
Together or alone to the above benzene sulfonic acid etc.
The alkoxy group to be bonded is an alkoxy having 1 to 12 carbon atoms.
Si group. The alkoxy group may be linear or branched.
However, it may be circular. At least one fluorine source
Child, preferably not more than 25 fluorine atoms are substituted
The Specifically, trifluoromethoxy group, pentafluoroe
Toxi group, heptafluoroisopropyloxy group, perf
Lorobutoxy group, perfluorooctyloxy group, perf
Rhododecyloxy group, perfluorocyclohexyloxy
Ci group and the like can be mentioned. Above all, all with fluorine
Preferred is a substituted perfluoroalkoxy group having 1 to 4 carbon atoms.
Good. With the above alkyl group alone or alone
The acyl group bonded to Zensulfonic acid or the like has 2 to 2 carbon atoms.
Those substituted with 12, 1 to 23 fluorine atoms
preferable. Specifically, trifluoroacetyl group, floroa
Cetyl group, pentafluoropropionyl group, pentafluoro
A benzoyl group etc. can be mentioned. Together with the alkyl group or alone
The acyloxy group bonded to benzenesulfonic acid, etc.
Substituted with 2 to 12 or 1 to 23 fluorine atoms
Is preferred. Specifically, trifluoroacetoxy
Group, fluoroacetoxy group, pentafluoropropionyl group
Name the xyl group, pentafluorobenzoyloxy group, etc.
You can. Together with the alkyl group or alone
As a sulfonyl group bonded to benzenesulfonic acid, etc.
Is substituted with a fluorine atom having 1 to 12 or 1 to 25 carbon atoms
What is done is preferable. Specifically, trifluorometa
Sulfonyl group, pentafluoroethanesulfonyl group,
-Fluorobutanesulfonyl group, perfluorooctanesulfur
Honyl group, pentafluorobenzenesulfonyl group, 4-to
Examples include rifluoromethylbenzenesulfonyl group
it can. With the above alkyl group alone or alone
The sulfonyloxy group bonded to Zensulfonic acid and the like
As, a fluorine atom having 1 to 12 or 1 to 25 carbon atoms
Those substituted with are preferred. Specifically, Triflo
Lomethanesulfonyloxy, perfluorobutanesulfoni
Ruoxy group, 4-trifluoromethylbenzenesulfonyl
An oxy group etc. can be mentioned. With alkyl group
Or it binds to benzenesulfonic acid etc. alone
The sulfonylamino group has 1 to 12 carbon atoms.
And substituted with 1 to 25 fluorine atoms
Is preferred. Specifically, trifluoromethanesulfonyl
Amino group, perfluorobutanesulfonylamino group, per
Fluorooctanesulfonylamino group, pentafluoroben
A zensulfonylamino group can be exemplified. Together with an alkyl group or alone
The aryl group bonded to benzenesulfonic acid, etc.
Substituted with fluorine atoms having 6 to 14 or 1 to 9 carbon atoms
What is done is preferable. Specifically, Pentaflorov
Enyl group, 4-trifluoromethylphenyl group, heptaph
Lolonaphthyl group, nonafluoroanthranyl group, 4-furo
Examples include lophenyl group and 2,4-difluorophenyl group.
be able to. Above or alone with alkyl group
Aralkyl group bonded to benzenesulfonic acid etc.
As, a fluorine atom having 7 to 10 carbon atoms and 1 to 15 carbon atoms.
Those substituted with are preferred. Specifically, Pentuff
Lolophenylmethyl group, pentafluorophenylethyl
Group, perfluorobenzyl group, perfluorophenethyl group, etc.
Can be mentioned. With or without alkyl groups
The above-mentioned alkane which binds to the above-mentioned benzenesulfonic acid alone.
The alkoxycarbonyl group has 2 to 13 carbon atoms, 1 to 1 carbon atoms.
Those substituted with 25 fluorine atoms are preferred.
Specifically, trifluoromethoxycarbonyl group, pentaf
Loroethoxycarbonyl group, pentafluorophenoxy
Rubonyl group, perfluorobutoxycarbonyl group, perf
Examples include lorooctyloxycarbonyl group.
The Of these anions, the most preferred
X^-Is a fluorine-substituted benzenesulfonate anion,
Among them, pentafluorobenzenesulfonate anion,
3,5-bis (trifluoromethyl) benzenesulfone
Acid anions are particularly preferred. In addition, the above fluorine-containing substituent
Alkyl sulfonic acid, benzene sulfonic acid,
Phthalene sulfonic acid or anthracene sulfonic acid is
In addition, linear, branched or cyclic alkoxy groups, acyl
Group, acyloxy group, sulfonyl group, sulfonyloxy
Group, sulfonylamino group, aryl group, aralkyl group,
Alkoxycarbonyl groups (these carbon number ranges are
Same as above), halogen (excluding fluorine), hydroxyl group,
It may be substituted with a tro group or the like. In the following, these general formulas (I) to (III)
The compounds represented and other specific examples are shown below.
It is not specified. In addition, each compound of the following specific examples
Combined with the cation part of another compound and the anion part of another compound
A compound can also be illustrated as a specific example of an acid generator. General formula
Specific examples of the compound represented by (I) are shown below. [0037] [Chemical formula 5][0038] [Chemical 6][0039] [Chemical 7]Specific examples of the compound represented by the general formula (II)
It is shown below. [0041] [Chemical 8][0042] [Chemical 9] Specific examples of compounds represented by formula (III)
Is shown below. [0044] Embedded image[0045] Embedded image[0046] Embedded imageOther than the compounds represented by formulas (I) to (III)
Specific examples of the compound are shown below. [0048] Embedded image [0049] Embedded image[0050] Embedded image [0051] Embedded image [0052] Embedded image[0053] Embedded imageThe compounds of general formula (I) and general formula (II) are
It can be synthesized by the following method. For example, aryl magne
Aryl Grignard reagents such as sium bromide
Triaryl obtained by reacting with nyl sulfoxide
Salt exchange of sulfonium halide with the corresponding sulfonic acid
The There is another way. For example, phenyl sulfoxide and
Corresponding aromatic compound is methanesulfonic acid / dipentapentoxide
Condensation and salt exchange using acid catalysts such as copper or aluminum chloride
There is a way to replace it. Diaryl iodonium salt and
Diaryl sulfide is condensed using a catalyst such as copper acetate.
In other words, it can be synthesized by a method of salt exchange. Above
In both methods, phenyl sulfoxide can be substituted with
Can be substituted on the ring, and such substituents are
It does not have to be. The compound of general formula (III) is periodate
Can be synthesized by reacting aromatic compounds with
It is. As an acid generator used in the present invention,
Is a sulfonate compound of N-hydroxyimide
Is preferred. N-hydroxyimide sulfonic acid ester
For example, the compound represented by the following general formula (PAG6)
And iminosulfonate derivatives. [0056] Embedded image R⁶⁰Is an alkyl optionally having a substituent.
Or an aryl group which may have a substituent.
The A⁶⁰Is an alkylene which may have a substituent
Group, cyclic alkylene group, alkenylene group, cyclic alkeni
Rene group or arylene group is shown. The above general formula (PAG
6) Medium, R⁶⁰Is an alkyl group which may have a substituent
(Preferably having 1 to 18 carbon atoms.
For example, methyl group, ethyl group, CF_Three, C_FourF₉Etc.
Or an aryl group which may have a substituent (preferably
Preferably, it has 6 to 14 carbon atoms.
An enyl group and a naphthyl group). A⁶⁰May have a substituent, al
Cylene group (preferably having 2 to 10 carbon atoms), cyclic alkyle
Group (preferably having 6 to 14 carbon atoms), alkenylene group
(Preferably 2 to 10 carbon atoms), cyclic alkenylene group
(Preferably having 6 to 14 carbon atoms) or an arylene group (preferably
Preferably it has 6 to 14 carbon atoms, such as benzene ring, naphthalene
A divalent group containing a ring). Where cyclic alkylene
Groups include cyclohexane residue, norbornane residue, etc.
Is mentioned. Cyclic alkenylene groups include cyclohexyl
Examples include xene residues and norbornene residues. Also,
Among the above groups, those having a cyclic structure constitute a ring
An oxygen atom or the like may be contained instead of the carbon atom. As substituents that these groups may have,
And preferably an alkyl group having 1 to 4 carbon atoms,
1-4 alkoxy groups, halogen atoms (fluorine atoms,
Chlorine atom, iodine atom), aryl having 6 to 10 carbon atoms
Group, alkenyl group having 2 to 6 carbon atoms, cyano group, hydro
Xyl group, carboxy group, alkoxy group having 2 to 5 carbon atoms
Examples include a rubonyl group, a nitro group, and a camphor residue. Hereinafter, the compound represented by the general formula (PAG6)
Specific examples of objects will be shown. The contents of the present invention are limited to these.
It is not a thing. [0061] Embedded image [0062] Embedded image[0063] Embedded image [0064] Embedded image[0065] Embedded image These compounds are for example G.F.Jaubert.
By Ber.,28, 360 (1895), D.E.Ames et al., J. Chem. S
oc., 3518 (1955) or by M.A. Stolberg et al., J. Amer. Chc
m. Soc.,79, 2615 (1957) etc.
It is. A cyclic N-hydroxyimide compound and R⁶⁰-SO
₂Cl (wherein R⁶⁰Has the same meaning as above. )
Sulfonic acid chloride prepared under basic conditions, for example
L. Baucr et al., J. Org. Chem.,twenty four, 1293 (1959) etc.
In accordance with the method described in 1. above. The acid generator used in the present invention has a total content of
0.1 to 20 times the solid content of the negative resist composition
% Is suitable, preferably 0.5-15% by weight,
It is preferably 1 to 12% by weight. (Other acid generators) In the present invention, the above-mentioned
Compounds represented by general formula (I) to general formula (III)
Or active radiation with a compound represented by (PAG6)
In combination with other compounds that decompose when irradiated with acid to generate acid
May be. General formula (I) to general formula (III) or (P
In addition to the compound represented by AG6), other compounds are used.
The general formula (I) to the general formula (III) or
Compound represented by (PAG6) and irradiation with actinic radiation
The ratio with other compounds that generate acid by decomposition by
100/0 to 20/80, preferably 90/10
-40/60, more preferably 80 / 20-50 / 50
It is. [2] Alkali-soluble resin In the present invention, the alkali-soluble resin is insoluble in water.
In the alkaline aqueous solution, soluble grafter (Al
Potassium soluble grafters) are used. Alkali soluble
Of alkali-soluble resin is 0.261N tetramethyl
Measured with ruammonium hydroxide (TMAH)
Those at 20 ° C./second or more (23 ° C.) are preferable. In particular
Preferably, it is 200 Å / sec or more (Å is ong
Strom). Alkali solubility graph used in the present invention
A tomer consists of a backbone polymer and a branch polymer. alkali
The soluble group has either a trunk polymer or a branch polymer.
It may be. The alkali-soluble group includes a polyhydroxy group.
Copolymer of styrene or hydroxystyrene
Those having a phenol moiety, polypinylbenzoic acid
Or has a carboxylic acid such as vinyl benzoic acid copolymer
Polystyrene sulfonic acid or styrene sulfate
Examples include sulfonic acid such as phonic acid copolymer
However, those having a phenol moiety are preferred. As a repeating unit forming a branched polymer
Is an alkali-soluble group-containing repeating unit, styrene,
Vinyl naphthalene, vinyl anthracene, etc. (copolymerization
(Depending on) hydrocarbon repeat unit, mono, di, trial
Repetitions derived from styrene derivatives such as coxistyrene
Repeat units are listed. As a repeating unit for forming a trunk polymer
Is an alkali-soluble group-containing repeating unit, styrene,
Such as pinylnaphthalene and vinylanthracene (copolymerization
Hydrocarbon repeat units, mono, di, trial
Repetitions derived from styrene derivatives such as coxistyrene
Repeat units are listed. Also, (meth) acrylic ester
Repeats derived from stealth, (meth) acrylamide, etc.
Repeat unit. The repeating unit constituting the branched polymer and the trunk polymer
The molar ratio with the repeating unit constituting the limer is usually 1:
99 to 99: 1, preferably 5:95 to 95: 5
The Reaction point spacing of branch polymer growth in trunk polymer
1 to 20 as the repeating unit of the trunk polymer on average
The number is preferably 1 to 5. Alkali-soluble groups are
40 to 99 mol% in all repeating units, preferably 45 to
Contains 95 mol%. Preferably, 40 to
90 mol%, 60-100 mol% on the branch polymer.
The weight average molecular weight of the alkali soluble grafter is preferred.
2,000 to 500,000, more preferably
3,000 to 300,000. Alkali-soluble
The amount of raftmer used is the total weight of the resist composition (solvent
Is usually 30 to 90% by weight based on
Or 50 to 80% by weight. Method for synthesizing alkali-soluble grafter
As a result, a polymerization initiation point is generated on the trunk polymer,
Method for polymerizing monomers, combining trunk and branch polymers
Method, trunk monomer and branch monomer (macromonomer)
There is a method of copolymerizing. Which of these three
Even when used, the alkali-soluble embryo of the present invention can be synthesized.
However, it is preferable to use the
Examples thereof include a method using a monomer. Graft poly
See “Graphs, Polymerization, and Applications”
Fumio Ide, 1977, Polymer publication society, or “Shintakabun
Child Experimental Science 2, Synthesis and Reaction of Polymers ”edited by the Society of Polymer Science, 1995
Years are listed in Kyoritsu Publishing Co., Ltd. Macro
The method using monomers is described in “Chemical Monomer Chemistry and Engineering
Is also described in Y. Yamashita et al., 1989, ICP.
The (2-1) Alkali solubility in the present invention
The graft mer is a structural unit represented by the following general formula (1)
It is preferable that the resin contains a trunk and / or a branch.
That's right. [0077] Embedded image Where R₁Is a hydrogen atom, halogen atom,
An ano group, an alkyl group or
Represents a loalkyl group. R₂Has a hydrogen atom and a substituent
Alkyl group, cycloalkyl group, aryl
Represents a group, an aralkyl group, or an acyl group. R_Three, R_Four
May be the same or different, hydrogen atom, halogen atom
Alkyl, cyano group, or substituent which may have a substituent
Group, cycloalkyl group, alkenyl group, aralkyl
Represents a group or an aryl group. A is a single bond, a substituent
An alkylene group, alkenylene group, cyclo
An alkylene group, an arylene group, -O-,-
SO₂-, -O-CO-R_Five-, -CO-O-R₆-,-
CO-N (R₇-R₈-Represents. R_Five, R₆, R₈Is the same
However, they may be different and may have a single bond or a substituent.
Alkylene group, alkenylene group, cycloalkylene group
Group, an arylene group alone, or these groups and
-Tel structure, ester structure, amide structure, urethane structure
Or at least one selected from the group of ureido structures
Represents a divalent group formed by combining species. R₇Is the same
However, they may be different and have a hydrogen atom or a substituent.
Alkyl group, cycloalkyl group, aralkyl
Represents a group or an aryl group. n represents an integer of 1 to 3.
Multiple R₂Or R₂And R_ThreeOr R_FourIs connected to the ring
May be formed. (2-2) Alkali-soluble graft
The following conditions (a) and
A repeating unit satisfying (b), and the following general formula
(3) ~ It is a resin having a repeating unit represented by (7)
Is also preferable. (A) an aromatic ring having 6 to 20 carbon atoms and
An ethylenically unsaturated group bonded via a contact or linking group
Less repeating units derived from monomers having
Have both. (B) π electrons of the aromatic ring and non-covalent electricity of substituents on the aromatic ring
The following relationship holds between the number of electrons in the child pair. [0080] [Expression 2] (Where Nπ represents the total number of π electrons, and N
_loneIs a straight chain having 1 to 12 carbon atoms as the substituent
, Branched or cyclic alkoxy groups, alkenyl
Oxy, aryloxy, aralkyloxy,
Or the total number of electrons in the lone pair of hydroxyl groups. 2 or more
The two adjacent alkoxy groups or hydroxyl groups are bonded to each other.
Together, they may form a ring structure of five or more members. ) [0082] Embedded image [0083] Embedded imageIn the general formulas (3) to (7), R
₁₀₁Represents a hydrogen atom or a methyl group. L is bivalent
Represents a linking group. Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, Ri,
Rj, Rk, and Rl are each independently a straight chain having 1 to 12 carbon atoms.
, Branched or cyclic alkyl groups, alkenyl
Group, aryl group, aralkyl group, or hydrogen atom
The In addition, these are connected to each other to form 5 having 24 or less carbon atoms.
You may form a ring more than a member. l, m, n, p, q, r, s, t, u, v, w,
x represents an integer from 0 to 3, l + m + n = 2,3, p + q + r = 0,1,
2,3, s + t + u = 0,1,2,3, v + w + x = 0,1,2,3. Other than the structural unit represented by the general formula (1)
In addition, other repeating structural units may be included. In the formula (1), R₁~ R_Four, R₇
As the alkyl group, for example, an alkyl group having 1 to 8 carbon atoms is used.
Specifically, a methyl group, an ethyl group, a pro
Pyr group, n-butyl group, sec-butyl group, hexyl group, 2-ethylene
Preferable examples include tilhexyl group and octyl group.
Yes. R₂~ R_Four, R₇The cycloalkyl group of can be monocyclic
It may be a polycyclic type. Monocyclic type has 3 to 8 carbon atoms
For example, cyclopropyl group, cyclopentyl group, cycl
A hexyl group can be preferably mentioned. Polycyclic and
For example, an adamantyl group, norbornyl group, iso
Boronyl group, dicyclopentyl group, α-pinel group, tri
Preferred examples include a cyclodecanyl group. R
_Three, R_FourAs the alkenyl group, for example, 2 to 8 carbon atoms
Specifically, a vinyl group,
Preferred examples include a ru group, a butenyl group, and a cyclohexenyl group.
Can be. R₂~ R_Four, R₇Examples of the aryl group of
For example, an aryl group having 6 to 15 carbon atoms, specifically
Is a phenyl group, a tolyl group, a dimethylphenyl group, 2,
4,6-trimethylphenyl group, naphthyl group, anthri
Preferable examples include a sulfur group. R₂~ R_Four, R₇
Examples of the aralkyl group include, for example, an aralkyl group having 7 to 12 carbon atoms.
Aralkyl group, specifically, benzyl group, phene
Preferable examples include til group and naphthylmethyl group.
Yes. R₁As the haloalkyl group, for example, charcoal
A haloalkyl group having 1 to 4 primes, specifically
Lolomethyl group, chloroethyl group, chloropropyl group,
Lolobutyl, bromomethyl, bromoethyl, etc. are preferred
I can mention it well. R₂As the acyl group, for example, carbon number 1
~ 8 acyl groups, specifically a formyl group,
Acetyl group, propanoyl group, butanoyl group, pivalloy
Preferable examples include a sulfur group and a benzoyl group. A, R_Five, R₆, R₈As an alkylene group of
Is preferably methylene which may have a substituent.
Group, ethylene group, propylene group, butylene group, hexile
And those having 1 to 8 carbon atoms, such as an ethylene group and an octylene group.
It is. A, R_Five, R₆, R₈As the alkenylene group of
Preferably an ethenylene group optionally having a substituent,
2-6 carbon atoms such as propenylene group, butenylene group
Can be mentioned. A, R_Five, R₆, R₈Cycloalkylene group
Is preferably a substituent, which may have a substituent.
5-8 carbon atoms such as lopentylene group, cyclohexylene group, etc.
Individuals are listed. A, R_Five, R₆, R₈The Arille
As the hydrogen group, preferably a phenylene group, a tolylene group,
And those having 6 to 12 carbon atoms such as a naphthylene group.
The As the substituents substituted for these groups,
Amino group, amide group, ureido group, urethane group, hydro
Having active hydrogen such as xyl group and carboxyl group
And halogen atoms (fluorine, chlorine, bromine,
Iodine atom), alkoxy group (methoxy group, ethoxy group,
Propoxy group, butoxy group, etc.), thioether group, reed
Group (acetyl group, propanoyl group, benzoyl group)
Etc.), acyloxy group (acetoxy group, propanoyloxy)
Si group, benzoyloxy group, etc.), alkoxycarbonyl
Group (methoxycarbonyl group, ethoxycarbonyl group,
Ropoxycarbonyl group, etc.), cyano group, nitro group, etc.
I can get lost. Especially amino group, hydroxyl group, carboxy
Those having an active hydrogen such as a sulfur group are preferred. Also, a plurality of R₂Or R₂And R_ThreeOr
R_FourAs the ring formed by bonding, a benzofuran ring,
Oxygen atoms such as benzodioxonol ring and benzopyran ring
4 to 7-membered rings containing It is represented by the general formula (1) used in the present invention.
Alkali-soluble grafter containing structural units
Is the following monomer (8), other polymerizable monomer if necessary
By radical polymerization and living anion polymerization
Can be obtained. [0095] Embedded image R in the general formula (8)₁, R₂, R_Three,
R_Four, A and n are R in the general formula (1).₁, R₂,
R_Three, R_Four, A and n. The alkali-soluble grafter has the general formula
(1) Resin consisting only of repeating structural units
May improve the performance of the resist of the present invention.
Other polymerizable monomers may be copolymerized for the purpose of
Yes. As copolymerizable monomers that can be used
Include the following: For example, other than the above
Acrylic esters, acrylamides, methacryl
Acid esters, methacrylamides, allyl compounds, vinyl
Nyl ethers, vinyl esters, styrenes, black
Addition polymerizable unsaturated bonds selected from tonic acid esters
It is a compound having one bond. Specifically, for example, acrylic ester
A class such as alkyl (the alkyl group has 1 to 1 carbon atoms)
0 is preferred) acrylate (eg acrylic
Methyl acetate, ethyl acrylate, propyl acrylate,
T-butyl crylate, amyl acrylate, acrylate
Chlohexyl, ethyl hexyl acrylate, acrylic acid
Octyl, acrylic acid-t-octyl, chloroethyla
Chryrate, 2-hydroxyethyl acrylate 2,2
-Dimethylhydroxypropyl acrylate, 5-hydride
Loxypentyl acrylate, trimethylolpropane
Monoacrylate, pentaerythritol monoacrylate
Glycidyl acrylate, benzyl acrylate
, Furfuryl acrylate, tetrahydrofurfuryl
Acrylates, etc.) aryl acrylates (e.g.
Phenyl acrylate); Methacrylic acid esters such as alkyl
(The alkyl group preferably has 1 to 10 carbon atoms.
) Methacrylate (eg methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, iso
Propyl methacrylate, t-butyl methacrylate,
Amyl methacrylate, hexyl methacrylate, chic
Rohexyl methacrylate, benzyl methacrylate,
Chlorbenzyl methacrylate, octyl methacrylate
2-hydroxyethyl methacrylate, 4-hydro
Xylbutyl methacrylate, 5-hydroxypentylme
Tacrylate, 2,2-dimethyl-3-hydroxypro
Pyrmethacrylate, trimethylolpropane monometa
Chryrate, pentaerythritol monomethacrylate
Glycidyl methacrylate, furfuryl methacrylate
, Tetrahydrofurfuryl methacrylate, etc.)
Aryl methacrylate (eg phenyl methacrylate)
, Cresyl methacrylate, naphthyl methacrylate
Etc.); Acrylamides such as acrylic
N-alkylacrylamide (as alkyl group
Are those having 1 to 10 carbon atoms, such as methyl,
Til, propyl, butyl, t-butyl, heptyl
Group, octyl group, cyclohexyl group, benzyl group,
Examples include droxyethyl group and benzyl group. ), N-A
Reel acrylamide (Examples of aryl groups include fluorine
Enyl, tolyl, nitrophenyl, naphthyl,
Cyanophenyl group, hydroxyphenyl group, carboxy
There are phenyl groups. ), N, N-dialkylacrylic
Luamide (As the alkyl group, it has 1 to 10 carbon atoms.
Such as methyl, ethyl, butyl, isobut
Til, ethylhexyl, cyclohexyl, etc.
The ), N, N-diarylacrylamide (aryl)
Examples of the group include a phenyl group. ), N-Me
Til-N-phenylacrylamide, N-hydroxye
Chill-N-methylacrylamide, N-2-acetoami
Doethyl-N-acetylacrylamide and the like; Methacrylamides such as methacryl
Amide, N-alkylmethacrylamide (with alkyl group
Such as those having 1 to 10 carbon atoms, such as methyl
Group, ethyl group, t-butyl group, ethylhexyl group, hydride
Examples include a loxyethyl group and a cyclohexyl group. ), N
-Aryl methacrylamide (As the aryl group,
There is a phenyl group. ), N, N-dialkyl methacrylate
Luamide (alkyl groups include ethyl, propyl
Groups and butyl groups. ), N, N-diarylmeta
Kurylamide (Aryl group includes phenyl group
is there. ), N-hydroxyethyl-N-methyl methacrylate
Luamide, N-methyl-N-phenylmethacrylami
, N-ethyl-N-phenylmethacrylamide and the like;
Allyl compounds such as allyl esters (eg vinegar
Allyl acid, allyl caproate, allyl caprylate, laur
Allyl phosphate, allyl palmitate, alicyclic stearate
Allyl benzoate, allyl acetoacetate, allyl lactate
And allyloxyethanol, etc .; Vinyl ethers such as alkyl vinyl
Ethers (eg hexyl vinyl ether, octyl
Ruvinyl ether, decyl vinyl ether, ethyl hex
Sil vinyl ether, methoxyethyl vinyl ether,
Ethoxyethyl vinyl ether, chloroethyl vinyl ether
Ether, 1-methyl-2,2-dimethylpropylvinyl
Ether, 2-ethylbutyl vinyl ether, hydroxy
Cyethyl vinyl ether, diethylene glycol vinyl
Ether, dimethylaminoethyl vinyl ether, die
Tylaminoethyl vinyl ether, butylaminoethyl
Vinyl ether, benzyl vinyl ether, tetrahydride
Rofurfuryl vinyl ether), vinyl aryl ether
Ether (eg vinyl phenyl ether, vinyl tolyl)
Ether, vinyl chlorophenyl ether, vinyl
2,4-dichlorophenyl ether, vinyl naphthyl ester
Ether, vinylanthranyl ether, etc.); Vinyl esters such as vinyl butyrate
, Vinyl isobutyrate, vinyl trimethyl acetate
, Vinyl diethyl acetate, vinyl valerate, vinyl
Nilcaproate, vinyl chloroacetate, vinyl di
Chloracetate, vinyl methoxyacetate, vinyl
Butoxy acetate, vinyl phenyl acetate, vinyl
Ruacetoacetate, vinyl lactate, vinyl-β-
Phenyl butyrate, vinyl cyclohexyl carboxy
Rate, vinyl benzoate, vinyl salicylate, chlor-anne
Vinyl benzoate, tetrachloro vinyl benzoate, naphtho
Vinyl acid, etc .; Styrenes such as styrene and alkyl
Styrene (eg, methylstyrene, dimethylstyrene)
, Trimethylstyrene, ethylstyrene, diethyls
Tylene, isopropyl styrene, butyl styrene, hex
Silstyrene, cyclohexylstyrene, decylstyrene
, Benzylstyrene, chloromethylstyrene, trif
Fluoromethylstyrene, ethoxymethylstyrene, ace
Toximethylstyrene), alkoxystyrene (eg
For example, methoxystyrene, 4-methoxy-3-methyls
Ethylene, dimethoxystyrene, etc.), halogen styrene
(For example, chlorostyrene, dichlorostyrene, trickle
Lol styrene, tetrachloro styrene, pentachloro
Tylene, bromostyrene, dibromostyrene, iodos
Tylene, fluorostyrene, trifluorostyrene, 2
-Bromo-4-trifluoromethylstyrene, 4-fluoro
Ol-3-trifluoromethylstyrene), carbo
Xylstyrene; Crotonates, such as croton
Alkyl (eg, butyl crotonate, crotonate
Xylyl, glycerin monocrotonate, etc.);
Dialkyl acids (eg, dimethyl itaconate, itaco
Diethyl acetate, dibutyl itaconate, etc.); maleic acid
Or dialkyl esters of fumaric acid (e.g.,
Dimethyl maleate, dibutyl fumarate, etc.), anhydrous
Maleic acid, maleimide, acrylonitrile, methacrylate
Examples include ronitrile and maleilonitrile. Others, general
For example, addition-polymerizable unsaturated compounds that are copolymerizable.
That's fine. Among them, carboxystyrene, N- (carbon
Ruboxyphenyl) acrylamide, N- (carboxy
Carboxyl group such as phenyl) methacrylamide
Monomer, maleimide, etc.
The monomer to be raised is preferred as a copolymerization component. The present invention
As the content of other polymerizable monomers in the resin
Is preferably 50 mol% or less based on the total repeating units.
More preferably, it is 30 mol% or less. The repetitive structure represented by the general formula (1) is as follows.
Preferred resin having a building unit (trunk and / or branch)
Although a specific example is shown, this invention is not limited to this.
Yes. [0109] Embedded image[0110] Embedded image[0111] Embedded image[0112] Embedded image[0113] Embedded image[0114] Embedded image[0115] Embedded image[0116] Embedded image[0117] Embedded image[0118] Embedded imageIn the above specific examples, n represents a positive integer. x,
y and z represent the molar ratio of the resin composition, and a resin composed of two components
Then, x = 10 to 95, y = 5 to 90, preferably x =
It is used in the range of 40-90, y = 10-60. Three
In a resin consisting of minutes, x = 10 to 90, y = 5 to 8
5, z = 5-85, preferably x = 40-80, y = 1
It is used in the range of 0-50 and z = 10-50. A repeating structural unit represented by the general formula (1)
The molecular weight of the alkali-soluble grafter having
Average, preferably 3,000 to 300,000
More preferably used in the range of 3,000 to 100,000
Is done. The molecular weight distribution is 1 to 10, preferably 1 to
3, more preferably those in the range of 1 to 1.5 are used.
The The smaller the molecular weight distribution, the higher the resolution and resist type.
And the side walls of the resist pattern are smooth and
Excellent funness. Repetitive structure represented by the general formula (1)
The content of the building unit is 5 to 100% with respect to the entire resin.
%, Preferably 10 to 90 mol%. It is represented by the general formula (1) used in the present invention.
Alkali-soluble grafter containing structural units
(Stem and / or branch), Macromolecules (1995), 2
8 (11), 3787-3789, Polym. Bull. (Berlin) (1990), 24
(4), 385-389, JP-A-8-286375.
It can be synthesized by the method described above. That is, radical weight
Or the living anion polymerization method.
Resoluble grafters can be obtained. These trees
Fats may be used alone or in combination.
good. Here, the weight average molecular weight is gel permeation.
With the polystyrene equivalent value of
Defined. (2-2) Alkali solubility in the present invention
One of the other preferable embodiments of the graft mer is the following conditions:
It contains a repeating unit that satisfies (a) and (b). (A) an aromatic ring having 6 to 20 carbon atoms and
An ethylenically unsaturated group bonded via a contact or linking group
Less repeating units derived from monomers having
Have both. (B) π electrons of the aromatic ring and non-covalent electricity of substituents on the aromatic ring
The relationship of the above formula (1) holds between the number of electrons in the child pair.
When. Here, Nπ represents the total number of π electrons, and N
_loneIs a straight chain having 1 to 12 carbon atoms as the substituent
, Branched or cyclic alkoxy groups, alkenyl
Oxy, aryloxy, aralkyloxy,
Or the total number of electrons in the lone pair of hydroxyl groups. 2 or more
The two adjacent alkoxy groups or hydroxyl groups are bonded to each other.
Together, they may form a ring structure of five or more members. In particular, Nπ + (1/2) N in the formula (1)
_loneGenerates secondary electrons to be in the range of 10-40
It is preferable because it has a structure that is easy to do. A preferred aromatic ring
Benzene, naphthalene, anthracene,
Enanthrene ring, biphenyl, etc.
Preferred substituents on the aromatic ring include hydroxyl, methoxy
Groups, ethoxy groups, isopropyl groups, etc.
The An aromatic ring having a total π electron Nπ of 10 or more (eg,
For example, naphthalene ring, anthracene ring or phenanthre
Ring, aromatic ring such as biphenyl)
Substituents on the ring are groups having no lone pair (N_lone= 0
Group), for example, hydrogen, saturated alkyl
And the like. (2-2-1) More specifically, alkali
The soluble grafter is represented by the general formulas (3) to (7).
It is preferable to have a repeating unit as a constituent
That's right. In the general formulas (3) to (7), R
₁₀₁Represents a hydrogen atom or a methyl group. L is bivalent
Represents a linking group. Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, Ri,
Rj, Rk, and Rl are each independently a straight chain having 1 to 12 carbon atoms.
, Branched or cyclic alkyl groups, alkenyl
Group, aryl group, aralkyl group, or hydrogen atom
The In addition, they are connected to each other to form 5 having 24 or less carbon atoms
You may form a ring more than a member. l, m, n, p, q, r, s, t, u, v, w,
x represents an integer from 0 to 3, l + m + n = 2,3, p + q + r = 0,1,
2,3, s + t + u = 0,1,2,3, v + w + x = 0,1,2,3. Examples of Ra, Rb and Rc are hydrogen, methyl
Group, ethyl group, propyl group, isopropyl group, butyl
Group, isobutyl group, t-butyl group, pentyl group, neope
Nethyl group, hexyl group, cyclohexyl group, octyl
Group, decyl group, dodecyl group, allyl group, benzyl group,
Examples include an phenyl group and a cumyl group. Also connected to each other
A methyl-substituted dioxol ring, an ethyl-substituted
Sole ring, phenyl substituted dioxole ring, dimethyl substitution
Examples are those that form dioxol and dioxane rings.
It is mentioned. Examples of Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, Rl
As hydrogen, methyl group, ethyl group, propyl group,
Sopropyl group, butyl group, isobutyl group, t-butyl
Group, pentyl group, neopentyl group, hexyl group, cyclo
Hexyl, octyl, decyl, dodecyl, ali
Group, benzyl group, phenyl group, cumyl group, etc.
It is. Rd to Rf, Rg to Ri, or Rj to Rl is a dioxole ring,
Methyl-substituted dioxol ring, ethyl-substituted disoxol
Ring, phenyl substituted dioxole ring, dimethyl substituted dioxy
Examples of those that form a sole ring or dioxane ring
It is done. Examples of L include a single bond, —CH₂-,-
COO-, -COOCH₂-, -OCH₂CH₂O-,-
OCH₂-, -CONH- and the like. Bonded to the main chain in each aromatic ring represented by Y
The position of the bond that binds to the substituent or the bond
Any one on the fragrance is acceptable. These are the monomers (9) to (13) below.
-Homopolymerization or other co-polymerization as above
It can be obtained by copolymerization with a comonomer. [0133] Embedded image [0134] Embedded imageIn the above, R₁a, R₁₀₁, Ra to Rl,
l, m, n, p, q, r, s, t, u, v, w, x are as defined above.
is there. Among the above, use a monomer having a hydroxyl group in the molecule.
When using, after protecting the hydroxyl group in advance
A method of removing the protecting group is preferred. In addition, with acid-decomposable groups
In the case of protection, a protective group is introduced after the completion of polymer synthesis.
The method is general. Preferred specific examples of these structures are listed below.
However, it is not limited to these. [0137] Embedded image[0138] Embedded image [0139] Embedded image [0140] Embedded image [0141] Embedded image [0142] Embedded image [0143] Embedded image[0144] Embedded image[0145] Embedded image[0146] Embedded image[0147] Embedded image[0148] Embedded image [0149] Embedded image [0150] Embedded image[0151] Embedded image [0152] Embedded image[0153] Embedded image[0154] Embedded image (2-2-2) Further, the al in the present invention
Potash soluble graft mer (stem and / or branch)
Partially alkyl etherized polyhydroxystyrene
And hydroxystyrene / styrene copolymers are also preferred
Yes. Partially alkyletherified polyhydro
In xylstyrene, alkyl etherified phenol
Nord unit (mol) / phenol unit (mol) is
The range of 1/99 to 30/70 is preferable. In hydroxystyrene / styrene copolymer
In which hydroxystyrene unit (mol) / styrene
The unit (mol) is preferably in the range of 70/30 to 95/5.
That's right. Hereinafter, the partial alkyl group according to the present invention will be described.
Preferred specific examples of tellurized polyhydroxystyrene
However, the present invention is not limited to this. [0159] Embedded image[0160] Embedded image [0161] Embedded image[0162] Embedded image [0163] Embedded image [0164] Embedded imageIn the present invention, the above (2-2-1) and
Alkali-soluble grafter according to (2-2-2)
Is used for radical polymerization, cationic polymerization, anionic polymerization, etc.
It can be synthesized by known methods. Combining corresponding monomers
Although it is most convenient to perform radical polymerization together,
Some monomers use cationic polymerization or anionic polymerization.
Can be synthesized more suitably. In addition, polymerization initiation species
Therefore, it is suitable when the monomer causes a reaction other than polymerization.
Polymerize monomers with appropriate protecting groups and remove them after polymerization
The desired polymer can be obtained by protecting. Ma
For polymers with alkoxy, the corresponding water
An etherification reaction can be performed on the hydroxyl group of a polymer having an acid group.
The desired polymer can also be obtained. Polymerization method
About experimental chemistry lecture 28 polymer synthesis, new experimental chemistry lecture
19 is described in polymer chemistry [I] and the like. The above alkali-soluble graftmer has a weight
The average molecular weight is preferably 3,000 to 300,000,
More preferably from 3,000 to 100,000, even more preferred
Specifically, it is 3,000 to 50,000. The molecular weight of the alkali-soluble graftmer
The distribution (Mw / Mn) is preferably 1.0 to 1.5.
This should make the resist especially sensitive.
Can do. It should be noted that the graft polymer having such molecular weight distribution
In the above synthesis method, living anionic polymerization is used.
Can be synthesized. In the resist composition of the present invention, the above-mentioned a
Along with Lucari soluble grafter, other alkali soluble
An adhesive resin can also be used in combination. Arca when used together
Examples of resoluble resins include novolak resins and hydrogenated resins.
Novolak resin, acetone-pyrogallol resin, o-po
Rehydroxystyrene, p-polyhydroxystyrene,
Hydrogenated polyhydroxystyrene, halogen or al
Kill-substituted polyhydroxystyrene, hydroxystyrene
-N-substituted maleimide copolymer, o / p-hydroxys
Tylene copolymer, against the hydroxyl group of polyhydroxystyrene
Partially O-alkylated (e.g. 5-30 mol%
O-methylated product, O- (1-methoxy) ethylated product, O
-(1-Ethoxy) ethylated product, O-2-tetrahydro
Pyranylated product, O- (t-butoxycarbonyl) methyl
Compound) or O-acylated compound (for example, 5-30 mol)
% O-acetylated product, O- (t-butoxy) carbo
Nylides, etc.), styrene-maleic anhydride copolymer,
Tylene-hydroxystyrene copolymer, α-methylstyrene
Len-hydroxystyrene copolymer, containing carboxyl groups
Mentioned methacrylic resin and its derivatives
However, it is not limited to these. Particularly preferred other alkali-soluble resins are:
Novolac resin and o-polyhydroxystyrene, p-
Polyhydroxystyrene and copolymers thereof, alkyl
Substituted polyhydroxystyrene, polyhydroxystyrene
Partial O-alkylation or O-acylation product,
Tylene-hydroxystyrene copolymer, α-methylstyrene
It is a lene-hydroxystyrene copolymer. The novolat
The resin is mainly composed of the following prescribed monomers and is acidic
By addition condensation with aldehydes in the presence of a catalyst.
Can be obtained. As the predetermined monomer, phenol, m
-Cresol, p-cresol, o-cresol, etc.
Resols, 2,5-xylenol, 3,5-xyleno
, 3,4-xylenol, 2,3-xylenol, etc.
Xylenols, m-ethylphenol, p-ethyl
Phenol, o-ethylphenol, pt-butylphenol
Enol, p-octylphenol, 2,3,5-tri
Alkylphenols such as methylphenol, p-meth
Xylphenol, m-methoxyphenol, 3,5-di
Methoxyphenol, 2-methoxy-4-methylpheno
, M-ethoxyphenol, p-ethoxyphenol
M, propoxyphenol, p-propoxypheno
, M-butoxyphenol, p-butoxyphenone
Alkoxyphenols such as 2-methyl-4-iso
Bisalkylphenols such as propylphenol, m
-Chlorophenol, p-chlorophenol, o-chloro
Lophenol, dihydroxybiphenyl, bisphenol
A, phenylphenol, resorcinol, naphtho
Hydroxy aromatic compounds such as
Can be used as a mixture, but is not limited to these
It is not a thing. Examples of aldehydes include formal.
Dehydr, paraformaldehyde, acetaldehyde,
Lopionaldehyde, benzaldehyde, phenylacetate
Toaldehyde, α-phenylpropyl aldehyde, β-
Phenylpropylaldehyde, o-hydroxybenzua
Rudehydr, m-hydroxybenzaldehyde, p-hydride
Roxybenzaldehyde, o-chlorobenzaldehyde
, M-chlorobenzaldehyde, p-chlorobenza
Rudehydr, o-nitrobenzaldehyde, m-nitrobe
Aldehyde, p-nitrobenzaldehyde, o-me
Tilbenzaldehyde, m-methylbenzaldehyde,
p-methylbenzaldehyde, p-ethylbenzalde
Hydride, pn-butylbenzaldehyde, furfura
, Chloroacetaldehyde and their acetals
Bodies such as chloroacetaldehyde diethyl acetal
Etc., but in these, formua
Preferably, aldehyde is used. These aldehydes
Can be used alone or in combination of two or more
The Acid catalysts include hydrochloric acid, sulfuric acid, formic acid, acetic acid,
An acid or the like can be used. The weight average molecular weight of the novolak resin is 1,
It is preferable that it is the range of 000-30,000.
If it is less than 1,000, the film loss after development of the irradiated part is large,
If it exceeds 30,000, the development speed will be reduced.
Yeah. Particularly preferred is the range of 2,000 to 20,000.
is there. In addition, the polyhydroxy other than the novolak resin
Weight average molecular weight of styrene, its derivatives and copolymers
Is 2000 or more, preferably 2000-30000,
More preferably, it is 2000-20000. here,
Weight average molecular weight is gel permeation chromatograph
Defined in terms of polystyrene equivalents. A used in combination with alkali-soluble grafter
The weight-average molecular weight of Lucari-soluble resin is 1,000-3.
It is preferably in the range of 10,000. 1,000 not
At full, the film loss after development of the irradiated area is large, 30,000
If this value is exceeded, the developing speed will be reduced. More suitable
It is in the range of 2,000 to 20,000. Sensitivity is
Particularly preferred alkali-soluble resin in terms of superiority
The weight average molecular weight ranges from 2,000 to 9,000
More preferably, it is the range of 2,500-9,000.
More preferably, in the range of 3,000 to 9,000
is there. Further, the molecular weight distribution of the alkali-soluble resin (Mw /
Mn) is 1.0 to 1.5 (monodisperse polymer).
However, it is preferable because development residue is reduced. Especially good sensitivity
Molecular weight distribution of the alkali-soluble resin particularly preferred in terms of
(Mw / Mn) is 1.0 to 1.4, more preferable.
1.0 to 1.3, and more preferably 1.0 to 1.3.
1.2. Here, the weight average molecular weight is gel perme
The value converted to polystyrene in chromatography
Is defined. Amount of alkali-soluble resin used in combination
Usually with respect to the weight of the alkali-soluble grafter
0 to 50% by weight. [3] Crosslinking agent In the negative resist composition of the present invention, an alkali-soluble resin is used.
A compound that crosslinks with an acid together with a fat and an acid generator.
(Referred to below as acid cross-linking agent or simply cross-linking agent)
The (3) -1 Use a phenol derivative as the cross-linking agent.
You can. Preferably, the molecular weight is 1200 or less, the molecule
Contains 3 to 5 benzene rings, and hydroxymethy
2 or more in total
Less hydroxymethyl and alkoxymethyl groups.
At least concentrate on one of the benzene rings or
To mention phenol derivatives that are separated and bonded
it can. By using such a phenol derivative
Thus, the effect of the present invention can be made more remarkable. Ben
The alkoxymethyl group bonded to the zen ring includes carbon atoms
Six or less are preferable. Specifically, methoxymethyl
Group, ethoxymethyl group, n-propoxymethyl group, i-
Propoxymethyl group, n-butoxymethyl group, i-but
Xymethyl group, sec-butoxymethyl group, t-butoxy
A cymethyl group is preferred. In addition, 2-methoxyethoxy
Group and 2-methoxy-1-propyl group,
Also preferred are xy-substituted alkoxy groups. These feces
Of the diol derivatives, particularly preferred are listed below. [0175] Embedded image [0176] Embedded image[0177] Embedded image [0178] Embedded image[0179] Embedded image(Wherein L¹~ L⁸Is the same but different
Hydroxymethyl group, methoxymethyl
Group or ethoxymethyl group. ) Phenol derivatives with a hydroxymethyl group are compatible
Phenolic compounds that do not have hydroxymethyl groups
(In the above formula, L¹~ L⁸Is a hydrogen atom) and
By reacting formaldehyde under a basic catalyst
Can be obtained. At this time, to prevent resinification and gelation
Therefore, the reaction temperature is preferably 60 ° C. or lower. Ingredients
Specifically, JP-A-6-282067 and JP-A-7-64.
It can be synthesized by the method described in No. 285 etc.
Yes. Phenol derivatives having alkoxymethyl groups
The phenol derivative with the corresponding hydroxymethyl group
By reacting a conductor and alcohol under an acid catalyst
Can be obtained. At this time, in order to prevent resinification and gelation
Furthermore, it is preferable to carry out the reaction at a temperature of 100 ° C. or lower. Ingredients
Specifically, it is described in European Patent EP632003A1 etc.
It can be synthesized by the method. In this way
Synthesized hydroxymethyl group or alkoxymethyl
Phenol derivatives having a group are stable in storage.
Preferable phenol derivatives with alkoxymethyl groups
The conductor is particularly preferable from the viewpoint of stability during storage. Hydro
2 in total including xymethyl group or alkoxymethyl group
Have the above, concentrate on any benzene ring, or
Such a phenol derivative formed by sorting and binding
May be used alone or in combination of two or more
May be used. (3) -2 In addition to the above phenol derivatives
The following compounds (i) and (ii) are used as cross-linking agents.
Can be used. (I) N-hydroxymethyl group, N-alkoxymethyl
Or a compound having an N-acyloxymethyl group
Stuff (Ii) Epoxy compound These crosslinking agents are described in detail below.
Light up. (I) N-hydroxymethyl group, N-alkoxymethyl
Or a compound having an N-acyloxymethyl group
As a product, European patent publication (hereinafter referred to as “EP-A”)
No. 0,133,216, West German Patent No. 3,63
No. 4,671, No. 3,711,264
Monomers and oligomers-melamine-formaldehyde condensation
Compounds and urea-formaldehyde condensates, EP-A
Alkoxy-substituted compounds disclosed in 0,212,482
Benzoguanamine-formaldehyde disclosed in
Examples include condensates. As a more preferable example,
At least two free N-hydroxymethyl groups, N
-Alkoxymethyl group or N-acyloxymethyl
And melamine-formaldehyde derivative
Of these, N-alkoxymethyl derivatives are particularly preferred.
Yes. (Ii) As an epoxy compound, one
Monomers, dimers and oligos containing the above epoxy groups
And polymer epoxy compounds
The For example, bisphenol A and epichlorohydrin
Reaction product of low molecular weight phenol-formaldehyde
Examples include reaction products of resin and epichlorohydrin.
The U.S. Pat. No. 4,026,705, UK
It is described and used in Japanese Patent No. 1,539,192.
The epoxy resin currently mentioned can be mentioned. In the present invention, the above phenol induction
The body is preferred. In addition to the above phenol derivatives, for example
Using other cross-linking agents (i) and (ii) as described above in combination
You can also. Use in addition to the above phenol derivatives
The ratio of the other crosslinking agent is 100/0 to 20/8 in molar ratio.
0, preferably 90/10 to 40/60, more preferably
Is 80 / 20-50 / 50. The cross-linking agent is 3% in the total resist composition solid content.
Used at an addition amount of ˜70 wt%, preferably 5 to 50 wt%
I can. If the added amount of the crosslinking agent is less than 3% by weight, the remaining film
The resolution decreases, and when it exceeds 70% by weight, the resolution decreases.
Furthermore, it is much preferred in terms of stability when storing resist solutions.
It ’s not. [4] (E) Organic basic compound Preferred organic basic compounds that can be used in the present invention
Is a compound that is more basic than phenol. During ~
However, nitrogen-containing basic compounds are preferred. Preferred chemical ring
Examples of the boundary include structures of the following formulas (A) to (E).
it can. [0187] Embedded image Here, R²⁵⁰ , R²⁵¹ And R²⁵² Is the same
One or different, a hydrogen atom, an atom having 1 to 6 carbon atoms
Rualkyl group, aminoalkyl group having 1 to 6 carbon atoms, carbon number
1-6 hydroxyalkyl groups or 6-20 carbon atoms
Represents a substituted or unsubstituted aryl group, wherein R
²⁵¹ And R²⁵² May combine with each other to form a ring.
R²⁵³ , R²⁵⁴ , R²⁵⁵ And R²⁵⁶ Are the same or different
Or an alkyl group having 1 to 6 carbon atoms. Further preferred compounds are different in one molecule.
Nitrogen-containing basification with two or more nitrogen atoms in chemical environment
Particularly preferably a substituted or unsubstituted amide.
If the compound contains both a mino group and a ring structure containing a nitrogen atom
Or a compound having an alkylamino group. Preferred specific examples include substituted or non-substituted
Substituted guanidines, substituted or unsubstituted aminopyridines
Substituted or unsubstituted aminoalkylpyridine,
Substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted
Substituted indazole, imidazole, substituted or unsubstituted
Substituted pyrazole, substituted or unsubstituted pyrazine, substituted
Or an unsubstituted pyrimidine, substituted or unsubstituted
Phosphorus, substituted or unsubstituted imidazoline, substituted or
Is unsubstituted pyrazoline, substituted or unsubstituted piperazi
Substituted, unsubstituted aminomorpholine, substituted
Or unsubstituted aminoalkylmorpholine.
It is. Preferred substituents are amino group, aminoalkyl
Group, alkylamino group, aminoaryl group, aryl group
Mino group, alkyl group, alkoxy group, acyl group, acylo
Xyl group, aryl group, aryloxy group, nitro group, water
An acid group and a cyano group. As particularly preferred compounds, guanidine,
1,1-dimethylguanidine, 1,1,3,3-teto
Lamethylguanidine, imidazole, 2-methylimida
Sol, 4-methylimidazole, N-methylimidazo
, 2-phenylimidazole, 4,5-diphenyl
Imidazole, 2,4,5-triphenylimidazole
, 2-aminopyridine, 3-aminopyridine, 4-a
Minopyridine, 2-dimethylaminopyridine, 4-dimethyl
Tilaminopyridine, 2-diethylaminopyridine, 2
-(Aminomethyl) pyridine, 2-amino-3-methyl
Pyridine, 2-amino-4-methylpyridine, 2-amino
No-5-methylpyridine, 2-amino-6-methylpyri
Gin, 3-aminoethylpyridine, 4-aminoethylpi
Lysine, 3-aminopyrrolidine, piperazine, N- (2
-Aminoethyl) piperazine, N- (2-aminoethyl)
L) Piperidine, 4-amino-2,2,6,6-tetra
Methylpiperidine, 4-piperidinopiperidine, 2-i
Minopiperidin, 1- (2-aminoethyl) pyrrolidi
, Pyrazole, 3-amino-5-methylpyrazole,
5-amino-3-methyl-1-p-tolylpyrazole,
Pyrazine, 2- (aminomethyl) -5-methylpyrazine
, Pyrimidine, 2,4-diaminopyrimidine, 4,6
-Dihydroxypyrimidine, 2-pyrazoline, 3-pyra
Zolin, N-aminomorpholine, N- (2-aminoethyl)
Chill) morpholine, etc.
It is not something. These nitrogen-containing basic compounds are used alone.
Or two or more are used together. For electron beam or X-ray
In a composition of a compound that generates more acid and an organic basic compound
The use ratio of (generates acid by electron beam or X-ray
Compound) / (organic basic compound) (molar ratio) = 2.5-
300 is preferable. The molar ratio is less than 2.5
May be low sensitivity and resolution may decrease,
If it exceeds 300, the resist will pass with time after irradiation until heat treatment.
Pattern fatness may increase and resolution may decrease.
is there. (Compound that generates acid by electron beam or X-ray)
/ (Organic basic compound) (molar ratio) is preferably 5.
It is 0-200, More preferably, it is 7.0-150. This
The addition of these nitrogen-containing basic compounds can
Improved stability over time (PCD stability and PED stability)
There is an effect to. PCD (Post Coating Delay)
Stability refers to an irradiation device after applying a resist composition to a substrate
The stability of the coating when left inside or outside the device,
PED (Post Exposure Delay) stability
Until the heating operation is performed later, in the irradiation device or device
It is the coating film stability when left outside. [5] Surfactants A surfactant is added to the negative resist composition of the present invention.
You can also. Specifically, polyoxyethylene laur
Ryl ether, polyoxyethylene stearyl ether
, Polyoxyethylene cetyl ether, polyoxye
Polyoxyethylene alkyl such as tylene oleyl ether
Luethers, polyoxyethylene octylphenol
Ether, polyoxyethylene nonylphenol ether
Polyoxyethylene alkyl allyl ethers such as
Polyoxyethylene / polyoxypropylene block co
Polymers, sorbitan monolaurate, sorbitan
Nopalmitate, sorbitan monostearate, sorbi
Tan monooleate, sorbitan trioleate, sol
Sorbitan fatty acid esters such as bitane tristearate
Polyoxyethylene sorbitan monolaurate, poly
Lioxyethylene sorbitan monopalmitate, polio
Xylethylene sorbitan monostearate, polyoxy
Ethylene sorbitan trioleate, polyoxyethylene
Polyoxyethylene such as sorbitan tristearate
Nonionic surfactants such as sorbitan fatty acid esters
Agent, EFTOP EF301, EF303, EF352
(Manufactured by Shin-Akita Kasei Co., Ltd.), Megafuck F171, F1
73 (Dainippon Ink Co., Ltd.), Florad FC43
0, FC431 (manufactured by Sumitomo 3M), Asahiga
Card AG710, Surflon S-382, SC101,
SC102, SC103, SC104, SC105, S
Fluorine surfactants such as C106 (Asahi Glass Co., Ltd.)
Organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.)
Manufactured by) or acrylic acid or methacrylic acid
(Co) polymerization polyflow No. 75, no. 95 (Kyoeisha
Manufactured by Yushi Chemical Co., Ltd.), Troisol S-366 (Toro)
Y Chemical Co., Ltd.). In addition,
At least one of silicon-based and silicon-based surfactants
It is preferable that the surfactant is blended. Also,
A surfactant containing both elementary and silicon atoms
It is also preferable. As these surfactants, for example
JP 62-36663, JP 61-226746, JP 61-2267
45, JP 62-170950, JP 63-34540, JP 7
-230165, JP-A-8-62834, JP-A-9-54432, JP
Hei 9-5988, U.S. Patent 5405720, U.S. Patent 5360692,
US patent 5529881, US patent 5296330, US patent 5436
098, U.S. Patent No. 5576143, U.S. Patent No. 5296143, U.S. Patent
Interface described in Japanese Patent No. 5294511 and US Pat. No. 5,842,451
And the following commercially available surfactants.
It can also be used as it is. As a commercially available surfactant
For example, F Top EF301, EF303 (Shin-Akita Kasei Co., Ltd.)
Manufactured), FLORARD FC430, 431 (manufactured by Sumitomo 3M),
Megafuck F171, F173, F176, F189, R08
Nuki Co., Ltd.), Surflon S-382, SC101, 102, 10
3, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-
Fluorosurfactant such as 366 (manufactured by Troy Chemical)
Or a silicon-type surfactant can be mentioned. Also
Polysiloxane polymer KP-341 (Shin-Etsu Chemical Co., Ltd.)
Can also be used as a silicon surfactant
The The amount of these surfactants contained in the composition of the present invention
Usually, 0.001 to 2 layers per 100 parts by weight of the solid content
Part by weight, preferably 0.01 to 1 part by weight. these
Surfactant may be added alone or some
It can also be added in combination. These surface activities
The addition of a curing agent increases the in-plane uniformity of the resist film.
There is an effect of improving the image power. [6] Solvent The negative resist composition of the present invention dissolves the above components.
It is dissolved in a solvent and coated on a support. Use here
Solvents include ethylene dichloride and cyclohexano
, Cyclopentanone, 2-heptanone, γ-butyro
Kuton, methyl ethyl ketone, ethylene glycol mono
Methyl ether, ethylene glycol monoethyl ether
, 2-methoxyethyl acetate, ethylene glycol
Lumonoethyl ether acetate, propylene glycol
Rumonomethyl ether, propylene glycol monomethyl
Ether ether, toluene, ethyl acetate, lactic acid
Chill, ethyl lactate, methyl methoxypropionate, etho
Ethyl xylpropionate, methyl pyruvate, pyruvin
Ethyl acetate, propyl pyruvate, N, N-dimethylform
Muamide, dimethyl sulfoxide, N-methylpyrrolide
And tetrahydrofuran are preferred.
Use alone or in combination. Particularly preferred solvents are
Propylene glycol monomethyl ether acetate /
Propylene glycol monomethyl ether ratio (weight
Ratio) is 100/0 to 30/70, preferably 100/0
-50/50, more preferably 100 / 0-80 / 20
It is a mixed solvent. [7] Dye In the negative resist composition of the present invention, if necessary, further
A dye or the like can be contained. As a suitable dye
There are oil-based dyes and basic dyes. Specifically, oily
Yellow # 101, Oil Yellow # 103, Oil Pin
# 312, Oil Green BG, Oil Blue BO
S, Oil Blue # 603, Oil Black BY, Oy
Le Black BS, Oil Black T-505
Manufactured by Ent Chemical Co., Ltd.), Crystal Violet
(CI42555), methyl violet (CI425)
35), Rhodamine B (CI45170B), Maracay
Togreen (CI42000), Methylene Blue (CI
52015). In the manufacture of precision integrated circuit elements, etc.
The pattern formation process on the strike film is performed using a substrate (eg, silicon
/ Transparent silicon dioxide cover, glass substrate, ITO substrate, etc.
Apply the negative resist composition of the present invention on a bright substrate)
And then irradiation using an electron beam, X-ray or EUV lithography system
Good by heating, developing, rinsing and drying
A resist pattern can be formed. Of the present invention
As a developer of the negative resist composition, sodium hydroxide is used.
Um, potassium hydroxide, sodium carbonate, sodium silicate
Inorganic aluminium, sodium metasilicate, aqueous ammonia, etc.
First, such as Lucaris, Ethylamine, n-Propylamine
Amines, diethylamine, di-n-butylamine, etc.
Secondary amines, triethylamine, methyldiethylamine
Tertiary amines such as dimethylethanolamine,
Alcoholamines such as ethanolamine, tetramethyl
Ammonium hydroxide, tetraethylammonium
Quaternary ammonium salts such as hydroxide and choline, pyro
Of cyclic amines such as alcohol, piperidine, etc.
An aqueous solution can be used. Further, the alkalis
Alcohols such as isopropyl alcohol,
Use an appropriate amount of nonionic surfactants.
You can also. Of these developers, the fourth
Monium salt, more preferably tetramethylammonium
Muhydroxide, choline. [0197] The present invention will be described in more detail with reference to the following examples.
However, the content of the present invention is not limited thereby.
Absent. 1. Composition example of composition material (1) Acid generator (C1) Tetramethylpentafluorobenzenesulfonate
Synthesis of ammonium salt Ice-cool 25 g of pentafluorobenzenesulfonyl chloride
Dissolve in 100 ml of lower methanol and add 25%
Add 100 g of lamethylammonium hydroxide aqueous solution
I added a lot. Stir at room temperature for 3 hours and pentafluorobe
Solution of tetramethylammonium sulfonate
Obtained. This solution is made into sulfonium salt, iodonium salt
Used for salt exchange with. (C2) Triphenylsulfonium penta
Synthesis of fluorobenzenesulfonate Diphenyl sulfoxide 50g to benzene 800ml
Dissolve, add 200 g of aluminum chloride to this, add 2
Refluxed for 4 hours. Slowly pour the reaction mixture into 2 liters of ice.
Add 400ml of concentrated hydrochloric acid and heat at 70 ° C for 10 minutes.
It was. This aqueous solution was washed with 500 ml of ethyl acetate and filtered.
After that, 200 g of ammonium iodide was added to 400 ml of water.
The dissolved one was added. The precipitated powder was collected by filtration and washed with water.
After washing with ethyl acetate and drying, triphenylsulfonate
70 g of umiozide was obtained. Triphenylsulfoni
Dissolve 30.5 g of umiozide in 1000 ml of methanol.
19.1 g of silver oxide was added to this solution and 4% was added at room temperature.
Stir for hours. Filter the solution and add excess pentaf.
Of lorobenzenesulfonic acid tetramethylammonium salt
The solution was added. Concentrate the reaction and dilute it with dichloromethane.
Dissolve in 500 ml and add 5% tetramethylan
Washed with aqueous ammonium hydroxide and water. Yes
After drying the organic phase over anhydrous sodium sulfate and concentrating,
Enylsulfonium pentafluorobenzenesulfonate
(I-1) was obtained. (C3) Di (4-t-amylphenyl) yo
Synthesis of donium pentafluorobenzenesulfonate 60 g of t-amylbenzene, 39.5 potassium iodate
g, Acetic anhydride 81g, Dichloromethane 170ml
66.8 g of concentrated sulfuric acid was slowly added dropwise to this under ice cooling.
It was. Stir for 2 hours under ice cooling and then for 10 hours at room temperature.
It was. Add 500 ml of water to the reaction solution under ice-cooling.
Extract with loromethane, organic phase with sodium bicarbonate and water
After washing and concentration, di (4-t-amylphenyl) yo
Donium sulfate was obtained. This sulfate is added in excess
Tetrafluorobenzenesulfonic acid tetramethylammoni
To the solution of um salt. Add 500 ml of water to this solution.
This is extracted with dichloromethane and the organic phase is 5% tetra
Wash with aqueous methylammonium hydroxide and water.
After purification and concentration, di (4-t-amylphenyl) io
Donium pentafluorobenzenesulfonate (III-
1) was obtained. Acid generator PAG-1 shown below and
PAG-2 can also be synthesized using the same method as above.
Yes. (2) Synthesis of alkali-soluble grafter Synthesis Example 1 p-t-Butoxystyrene Macromonomer (Mw
2600; terminal methacrylate: Toagosei Co., Ltd.) 17.6g, p-
Dissolve 4.4 g of t-butoxystyrene in dry THF and add nitrogen.
Heated to 70 ° C. under a stream of air. Wako Pure Chemicals azo radical opening
Initiator V-601 and 80 mol% of the total amount of the monomers were added. 6:00
After the reaction, the reaction solution was diluted with THF and methanol
Precipitated in and purified to remove the polymer. In the usual way
It was further decomposed with acid to obtain GP1. Weight by GPC measurement
Average molecular weight (Mw) and molecular weight dispersity (Mw / Mn) were determined. (Synthesis Example 2) p-t-but in Synthesis Example 1
Instead of xylstyrene, 3,4-dimethoxystyrene
(GP2) was obtained in the same manner except that it was used. (Synthesis Example 3) p-t-but in Synthesis Example 1
Use 1-vinylnaphthalene instead of xylstyrene
(GP3) was obtained in the same manner except that was used. Synthesis Example 4 p-t-but in Synthesis Example 1
Use m-t-butoxycystelen instead of xylstyrene.
(GP4) was obtained in the same manner except for the above. (Synthesis Example 5) p-t-but in Synthesis Example 1
Instead of 4.4 g of xylstyrene, 2 g of p-vinylbenzoic acid
(GP5) was obtained in the same manner except that it was used. Synthesis Example 6 p-t-but in Synthesis Example 1
Except for using styrene instead of xylstyrene
In the same manner, (GP6) was obtained. Synthesis Example 7 (GP1) 12.5 g of acetone
Dissolve in 50 ml, potassium carbonate 0 · 57 g and ethyl iodide 3
-2g was added and it heated and refluxed for 6 hours. The reaction solution was filtered
After that, the filtrate is added dropwise to 1 L of pH 3 acetic acid aqueous solution to cause precipitation.
The temple was collected by filtration. After vacuum drying, acetone / to
Separation and precipitation using xane to remove low molecular weight components (G
P7) was obtained. (Synthesis Example 8) p-t-butoxystyrene mac
Use styrene macromonomer instead of monomer
In the same manner as in Synthesis Example 1, (GP8) was obtained. (Synthesis Example 9) GP1 was changed to acetone / hexane.
To separate the precipitate and add more hexane to the concentrated phase.
The resulting dilute phase is concentrated to produce a polymer with a narrow molecular weight distribution (G
P9) was obtained. (Synthesis Example 10) Polyhydroxystyrene (VP-5000: Japan
Soda) 10g dissolved in methanol, p-t-butoxy
Len 10g, Wako Pure Chemicals azo radical initiator V-601
Add 10 mol% of the total amount of monomer, deaerate,
Dilute the reaction solution with THF and dilute with THF in methanol.
The polymer was taken out by purification. By the ordinary method
Decomposition with phosphoric acid gave (GP10). (Synthesis Example 11) p-t-butoxystyrene was mixed with V-601 and
Polymerized in the presence of Lukabutetal, terminal hydrosyl poly
Got mer. Tosylation of terminal hydroxyl group with tosyl chloride
In the presence of a base, polyhydroxystyrene (VP-5000:
Reacted with Nippon Soda). Treat the removed polymer with acid.
To obtain (GP11). (Alkali Solubility Graph of Synthesis Examples 1 to 11)
Topolymer) Alkali-soluble in the present invention of Synthesis Examples 1-11
The graft polymer is shown below. [0211] Embedded image[0212] Embedded image[0213] Embedded image [0214] Embedded image(3) Crosslinking agent Synthesis of crosslinking agent [HM-1] 1- [α-methyl-α- (4-hydroxyphenyl) ester
Til] -4- [α, α-bis (4-hydroxypheny
Le) ethyl] benzene 20 g (T, manufactured by Honshu Chemical Industry Co., Ltd.)
risp-PA) in 10% aqueous potassium hydroxide solution
Stir and dissolve. Next, while stirring this solution, 3
60ml of 7% formalin aqueous solution over 1 hour at room temperature
Gradually added. After further stirring for 6 hours at room temperature, dilute sulfur
Throwed into acid aqueous solution. The precipitate was filtered and washed thoroughly with water
Then, by recrystallization from 30 ml of methanol,
Phenol derivatives having a hydroxymethyl group of the structure
20 g of white powder of [HM-1] was obtained. The purity is 92%
(Liquid chromatography method). [0216] Embedded image Synthesis of cross-linking agent [MM-1] Fe of hydroxymethyl group obtained in the above synthesis example.
20 g of a diol derivative [HM-1] in 1 liter of methanol
The solution was stirred and heated to dissolve. Then into this solution
1 ml of concentrated sulfuric acid was added, and the mixture was heated to reflux for 12 hours. End of reaction
Thereafter, the reaction solution was cooled, and 2 g of potassium carbonate was added. This
After fully concentrating the mixture, add 300 ml of ethyl acetate.
Yeah. This solution is washed with water and concentrated to dryness.
A phenol derivative having a methoxymethyl group of the following structure:
22 g of a white solid of conductor [MM-1] was obtained. Purity is 90
% (Liquid chromatography method). [0218] Embedded imageFurther, the following phenols were similarly obtained.
Derivatives were synthesized. [0220] Embedded image [0221] Embedded image[0222] Embedded image2. Example <Electron Beam Irradiation> (1) Application of resist Preparation of a photoresist composition solution having the composition shown in Table 1
And filtered through a 0.1 μm filter. Each Regis
8 inch silicon using a spin coater
Apply on wafer, vacuum adsorption type for 90 seconds at 120 ° C
Resist with a thickness of 0.3μm after drying on a hot plate
A membrane was obtained. (2) Preparation of resist pattern An electron beam lithography apparatus (acceleration voltage 50 Ke
Irradiation was performed using V). 110 ° C after irradiation
Heat for 60 seconds on the vacuum adsorption type hot plate of
2.38 wt% tetramethylammonium hydrooxy
Immerse in side (TMAH) aqueous solution for 60 seconds, 30 seconds
Rinse with water and dry. Cross-sectional shape of the obtained pattern
Were observed with a scanning electron microscope. (3) Evaluation method [Sensitivity and Resolution] Sensitivity is 0.20 μm line (line
Feel the minimum dose when resolving
Limit resolution at that dose (line and spectrum)
The resolution was defined as “Separate resolution”. 0.20 μm line
(Line: Space = 1: 1)
Is the resolution of the limit and the dose at that time is the sensitivity and
did. [Number of development defects] The resist pattern obtained as described above.
About K.K.
Obtained by measuring the number of development defects with LA-2112 machine
The primary data value was defined as the number of development defects. Development defects are observed
For those having a development defect number of 1 to 10, A,
B of 11 to 499 and C of 500 or more. So
The results are shown in Tables 1-2. [0224] [Table 1][0225] [Table 2] Details of each component shown in Tables 1 and 2 are as follows.
Shown in [0227] Embedded imageP-101: Poly (p-hydroxystyrene)
Ren) Mw 10,000 Mw / Mn = 1.4 P-102: Novolac resin m-cresol / p-cresol = 45/55 (mole
ratio) Mw 6,500 [0229] Embedded image [0230] Embedded image [0231] Embedded image (Solvent) PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether
acetate (Organic basic compounds) B-1: 2,4,5-Triphenylimidazole B-2: 1,5-diazabicyclo [4.3.0] nona
5-ene B-3: 4-Dimethylaminopyridine B-4: 1,8-diazabicyclo [5.4.0] unde
Car-7-ene B-5: N-cyclohexyl-N′-morpholinoethylthio
Oura (Surfactant) W-1: Troisol S-366 (Troy Chemical Co., Ltd.)
Made) W-2: Mega Fuck F-176 (Dainippon Ink
(Gaku Kogyo) W-3: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.)
(Made by a company) W-4: Polysiloxane polymer KP-341
Koshi Chemical Industry Co., Ltd.) W-5: Surflon S-382 (Asahi Glass Co., Ltd.) Examples 1, 8, 9, 18, 19, 20 and
22, the organic basic compound is respectively B-2,
When changed to B-3, B-4, and B-5, the same
Etc. were obtained. In addition, Examples 1, 8, 9, 18,
In 19, 20 and 22, the surfactant is W
-2, W-3, W-4, W-5
B) Equivalent performance was obtained. Examples 1, 8, 9, 18,
19, 20, and 22, the solvent is propylene glycol
Monomethyl ether acetate / propylene glycol
Change to 80/20 (wt / wt)
As a result, similar effects were obtained. From the results shown in Table 2, the resist composition of the present invention.
High sensitivity, high resolution and reduced development defects
I understand. 3. Example <same size X-ray irradiation> Each resist composition of Example 1 and Comparative Example 1 is used.
In the same manner as in Example 1 above, the film thickness is 0.4.
A 0 μm resist film was obtained. Next, equal magnification X-ray irradiation device
Example 1 except that (gap value; 20 nm) was used.
In the same manner as in Example 1 above,
evaluated. As a result, almost the same as Example 1 and Comparative Example 1
Results were obtained. [0237] According to the present invention, the present invention has high sensitivity and high resolving power.
For negative electron beam, X-ray or EUV with reduced image defects
A chemically amplified resist composition can be provided.

Claims (1)

1. A negative resist composition comprising (A) an alkali-soluble resin, (B) a compound that generates an acid upon irradiation with actinic radiation, and (C) a cross-linking agent. A negative resist composition, wherein the alkali-soluble resin is a graft polymer.