韩国专利KR20010050483A Resist Compositions and Patterning Process

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专利摘要:
The present invention relates to a resist material for ArF excimer laser containing a base resin, an acid generator and a solvent, wherein the acid generator is a sulfonium salt represented by the following general formula (1). Wherein R 1 represents a hydroxyl group, a nitro group or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 15 carbon atoms which may contain O, N or S atoms, and two R 1 form a ring In which case R 1 represents a linear, branched or cyclic divalent hydrocarbon group having 1 to 15 carbon atoms which may contain O, N or S atoms, K − represents a non-nucleophilic counter ion, x Represents 1 or 2, and y represents an integer of 0 to 3. Since the resist material of the present invention is sensitive to ArF excimer laser light and is excellent in sensitivity and resolution, and can be thickened, it is also advantageous for etching, and it is possible to easily form a fine pattern perpendicular to the substrate. Have
公开号:KR20010050483A
申请号:KR1020000054385
申请日:2000-09-16
公开日:2001-06-15
发明作者:쯔네히로 니시；요이찌 오사와；쥰 하따께야마
申请人:카나가와 치히로；신에쓰 가가꾸 고교 가부시끼가이샤；
IPC主号:

专利说明:

Resist Materials and Pattern Forming Method {Resist Compositions and Patterning Process}
The present invention relates to a resist material for ArF excimer laser and (2) a pattern formation method using the resist material, which comprises (1) a specific sulfonium salt as an acid generator.
In recent years, with the higher integration and higher speed of LSI, finer pattern rules have been required, and far-infrared lithography is promising as a next-generation fine processing technology. Among them, port lithography using ArF excimer laser light as a light source is an indispensable technique for ultra-fine processing of 0.2 μm or less, and its implementation is urgently desired.
In photolithography using ArF excimer laser light as a light source, there is a demand for a highly sensitive resist material capable of exhibiting sufficient resolution with a small exposure amount in order to prevent deterioration of an expensive optical material. As a countermeasure for realizing a highly sensitive resist material, it is most common to select what is high transparency at wavelength 193nm as each composition. For example, for the base resin, polyacrylic acid and its derivatives, norbornene-maleic anhydride alternating polymers, polynorbornene and metathesis ring-opening polymers and the like have been proposed, and in view of increasing the transparency of the resin monomers, I am getting some results. However, it was a reality that when the transparency was increased for the acid generator, the acid generation efficiency was lowered, and as a result, the degree was reduced, or the thermal stability and the storage stability were lacking, and thus, it was not obtained enough for practical use.
For example, the alkylsulfonium salts proposed in Japanese Patent Laid-Open Nos. 7-25846, 7-28237, 8-27102 and the like have very high transparency, insufficient acid generation efficiency, and thermal stability. There was also a problem, which was not preferable. Alkyl arylsulfonium salts proposed in Japanese Patent Application Laid-open No. Hei 10-319581 have high sensitivity due to a good balance between transparency and acid generation efficiency, but lack thermal stability and storage stability. Although the arylsulfonium salt effective in photolithography using KrF excimer laser light is excellent in acid generation efficiency, thermal stability, and storage stability, the transparency obtained is significantly low, and the pattern obtained in exposure-developing has become a severe taper shape. In order to supplement the transparency, there is also a countermeasure to reduce the thickness of the resist, but in this case, the etching resistance of the resist film is significantly lowered, which is not suitable as a pattern forming method.
This invention is made | formed in view of the said situation, (1) The high resolution resist material which mix | blended the acid generator which was highly sensitive to ArF excimer laser beam, and was excellent in thermal stability and storage stability, (2) using this resist material It is an object to provide a pattern formation method.
MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, as a result, the sulfonium salt represented by following formula (1) is highly sensitive to ArF excimer laser beam, and has sufficient thermal stability and storage stability, and the resist material which mix | blended this It has been found that it has high resolution and that this resist material is very effective for precise microfabrication.
That is, the present invention provides the following resist material.
[I] A resist material for an ArF excimer laser, comprising a base resin, an acid generator, and a solvent, wherein the acid generator is a sulfonium salt represented by the following general formula (1).
<Formula 1>
Wherein R ¹ represents a hydroxyl group, a nitro group, or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 15 carbon atoms which may contain O, N or S atoms, and two R ¹ represent a ring In which case R ¹ represents a linear, branched or cyclic divalent hydrocarbon group having 1 to 15 carbon atoms which may contain O, N or S atoms, K ⁻ represents a non-nucleophilic counter ion, x represents 1 or 2, and y represents the integer of 0-3.
[II] The resist material according to [I], wherein the base resin is a polymer compound having a weight average molecular weight of 1,000 to 500,000 having a repeating unit represented by the following formula (2).
In the above formula, R ¹ represents a hydrogen atom, a methyl group or CH ₂ CO ₂ R ³ , R ² represents a hydrogen atom, a methyl group or CO ₂ R ³ , and R ³ is a straight, branched or cyclic chain having 1 to 15 carbon atoms. represents an alkyl group, R ⁴ represents a monovalent hydrocarbon group containing a hydrogen atom or a carboxyl or hydroxyl group having 1 to 15 carbon atoms, R ⁵ to R one or more of the ⁸ is a monovalent group containing a carboxyl or hydroxyl group having 1 to 15 carbon atoms Hydrocarbon groups, the remainder each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, and R ⁵ to R ⁸ may form a ring with each other, in which case R ⁵ to R ⁸ At least one represents a divalent hydrocarbon group containing a carboxyl group or a hydroxyl group having 1 to 15 carbon atoms, and the rest are each independently a single bond or a 1 to 15 carbon atom. Chain, branched denotes the ground, of the cyclic alkylene group, R ⁹ is C 3 -C 15 -CO ₂ - represents a monovalent hydrocarbon-containing partial structure, R ¹⁰ to R ¹³ is one or more of the carbon number of 2 to l5 - A monovalent hydrocarbon group containing a CO ₂ -part structure, each independently represent a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms, and R ¹⁰ to R ¹³ may form a ring with each other; In this case, at least one of R ¹⁰ to R ¹³ represents a divalent hydrocarbon group containing a 1 to 15 carbon atoms -CO ₂ -partial structure, the rest are each independently a single bond or a straight chain having 1 to 15 carbon atoms, Represents a branched or cyclic alkylene group, R ¹⁴ represents an alkyl group containing a polycyclic hydrocarbon group or a polycyclic hydrocarbon group having 7 to 15 carbon atoms, R ¹⁵ represents an acid labile group, k represents 0 or 1, and a1, a2, a3, b1, b2, b3, c1, c2, c3, d1, d2, d3, e are numbers of 0 or more and less than 1, and a1 + a2 + a3 + b1 + b2 + b3 + c1 + c2 + c3 + d1 + d2 + d3 + e = 1 is satisfied.
Moreover, this invention provides the following pattern formation method.
[III] a step of applying the resist material according to the above [I] or [II] onto a substrate, a step of exposing the light with a wavelength of 193 nm through a photomask after the heat treatment, and heat treatment as necessary. The pattern formation method characterized by including the process of image development using a developing solution.
Sulfonium salt represented by the formula (1) is very sensitive to the ArF excimer laser light, it is possible to generate a sufficient amount of acid in a small compounding amount. Therefore, the resist material which mix | blended this has high sensitivity and high transparency, and since the pattern obtained by exposure-developing has high spherical shape and does not need thin film formation, it is advantageous also about etching. In addition, the lack of thermal stability and storage stability, which were disadvantages of conventional alkylsulfonium salts and alkylarylsulfonium salts, were also eliminated.
In the sulfonium salt represented by the formula (1), one to two aryls are introduced at the expense of transparency to some extent, whereby the acid generation efficiency is greatly improved, and as a result, the sensitivity can be increased. Sensitivity to light with a wavelength of 193 nm can be improved to three times or more than an arylsulfonium salt when the transmittance of the resist film is collectively compared. Moreover, the problem of the thermal stability and the storage stability which the conventional product contained was overcome by selecting methyl which has no adjacent carbon and hydrogen on this carbon as alkyl.
In addition, the sulfonium salt represented by the formula (1) is only highly sensitive to ArF excimer laser light, and is not useful in photolithography using, for example, KrF excimer laser light having a wavelength of 248 nm.
Hereinafter, the present invention will be described in more detail.
The resist material of this invention contains the sulfonium salt represented by following formula (1).
<Formula 1>
In the above formula, R ¹ represents a hydroxyl group, a nitro group, or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 15 carbon atoms which may include O, N or S atoms, specifically methyl, ethyl, propyl Group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, ethylcyclopentyl group, butyl Alkyl groups, such as a cyclopentyl group, an ethylcyclohexyl group, a butylcyclohexyl group, an adamantyl group, an ethyl adamantyl group, and a butyl adamantyl group, the alkoxy group which couple | bonded the said alkyl group etc. through -0-, and -0- (CO An alkylcarbonyloxy group bonded to the alkyl group and the like through)-, an alkoxycarbonyloxy group bonded to the alkyl group and the like through -0- (C0) -0- and -O- (SO ₂ )- Alkylsulfonyloxy group which couple | bonded the alkyl group etc., Alkoxy which couple | bonded the said alkyl group etc. through-(CO) -0- Formyloxy group, a carboxyl group, etc. can be illustrated besides the alkylthio group etc. which couple | bonded the said alkyl group etc. through the carbonyloxy group and -S-, and each of the hydrogen atoms of the said group is the same or separate each said Groups having 1 to 15 carbon atoms substituted with groups can be exemplified. In addition, some of the hydrogen atoms of these groups may be substituted with groups containing O, N or S atoms such as hydroxyl group, oxo group, nitro group, mercapto group and the like. In addition, two R ¹ may form a ring, in which case R ¹ represents a linear, branched or cyclic divalent hydrocarbon group having 1 to 15 carbon atoms which may include O, N or S atoms, and Examples include methane, ethane, propane, isopropane, butane, isobutane, pentane, isopentane, hexane, cyclopentane, cyclohexane, ethylcyclopentane, butylcyclopentane, ethylcyclohexane, butylcyclohexane, adamantane, ethyl -O-, -O- (CO)-, -O- to a bivalent group and one to two bonds of the divalent group except two hydrogen atoms at arbitrary positions of alkanes such as adamantane and butyl adamantane (CO) -O-, -O- (SO 2) -, - (CO) -O-, via the same or different 1 to 2 selected from the dog -S- can be cited a group. K ⁻ represents a non-nucleophilic counter ion, and specifically, halide ions such as chloride ions and bromide ions, triflate, fluoro such as 1,1,1-trifluoroethanesulfonate and nonafluorobutanesulfonate Alkyl sulfonates, such as alkyl sulfonate, tosylate, benzene sulfonate, 4-fluorobenzene sulfonate, and 1,2,3,4,5-pentafluorobenzene sulfonate, alkyl, such as a mesylate and butane sulfonate Sulfonates can be exemplified. x is 1 or 2, y is 0-3, Preferably it is 0-2, More preferably, the integer of 0-1 is represented.
Although the specific example of the sulfonium salt represented by the said General formula (1) mix | blended with the resist material of this invention is shown below, it is not limited to this.
The compounding quantity of the sulfonium salt of the said Formula (1) is 0.1-15 parts with respect to 100 parts (weight part, below same) of base resin especially 0.5-8 part. If the amount is too small, the degree of reduction may be reduced. If the amount is too large, the transparency may decrease and the resolution performance of the resist material may decrease.
Moreover, this invention can be made into the said resist material containing the polymer compound of the weight average molecular weights 1,000-500,000, Preferably 5,000-100,000 which have a repeating unit represented by following General formula (2) as a base resin.
<Formula 2>
In the above formula, R ¹ represents a hydrogen atom, a methyl group or CH ₂ CO ₂ R ³ . R ² represents a hydrogen atom, a methyl group or CO ₂ R ³ . R ³ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, tert -Amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, ethylcyclopentyl group, butylcyclopentyl group, ethylcyclohexyl group, butylcyclohexyl group, adamantyl group, ethyl adamantyl group And a butyl adamantyl group etc. can be illustrated. R ⁴ represents a monovalent hydrocarbon group (preferably a linear, branched or cyclic alkyl group) containing a hydrogen atom or a carboxyl group or a hydroxyl group having 1 to 15 carbon atoms, specifically, carboxyethyl, carboxybutyl, carboxycyclopentyl , Carboxycyclohexyl, carboxynorbornyl, carboxyadamantyl, hydroxyethyl, hydroxybutyl, hydroxycyclopentyl, hydroxycyclohexyl, hydroxynorbornyl, hydroxyadamantyl group and the like can be exemplified. . At least one of R ⁵ to R ⁸ represents a monovalent hydrocarbon group (preferably a linear, branched or cyclic alkyl group) containing a carboxyl or hydroxyl group having 1 to 15 carbon atoms, and the remaining ones each independently represent a hydrogen atom or carbon number. 1 to 15 linear, branched or cyclic alkyl groups are represented. As a monovalent hydrocarbon group containing a C1-C15 carboxyl group or a hydroxyl group, specifically, carboxy, carboxymethyl, carboxyethyl, carboxybutyl, hydroxymethyl, hydroxyethyl, hydroxybutyl, 2-carboxyethoxycarbonyl , 4-carboxybutoxycarbonyl, 2-hydroxyethoxycarbonyl, 4-hydroxybutoxycarbonyl, carboxycyclopentyloxycarbonyl, carboxycyclohexyloxycarbonyl, carboxynorbornyloxycarbonyl, Carboxyadamantyloxycarbonyl, hydroxycyclopentyloxycarbonyl, hydroxycyclohexyloxycarbonyl, hydroxy norbornyloxycarbonyl, hydroxyadamantyloxycarbonyl and the like can be exemplified. Specifically as a C1-C15 linear, branched, cyclic alkyl group, the thing similar to what was illustrated by R <^3> can be illustrated.
R ⁵ to R ⁸ may form a ring with each other, in which case at least one of R ⁵ to R ⁸ may be a divalent hydrocarbon group (preferably straight or branched) containing a carboxy group or hydroxyl group having 1 to 15 carbon atoms. Alkylene group), and the rest each independently represents a single bond or a linear, branched, or cyclic alkylene group having 1 to 15 carbon atoms. As a bivalent hydrocarbon group containing a C1-C15 carboxyl group or a hydroxyl group, the thing etc. which removed one hydrogen atom specifically from what was illustrated by the said monovalent hydrocarbon group containing a carboxyl group or a hydroxyl group can be illustrated. As a C1-C15 linear, branched, cyclic alkylene group, what specifically removed one hydrogen atom from what was illustrated by R <^3> , etc. can be illustrated. R ⁹ represents a monovalent hydrocarbon group containing a C3-C5 -CO ₂ -partial structure, specifically 2-oxooxolan-3-yl, 4,4-dimethyl-2-oxooxolane-3- One, 4-methyl-2-oxooxan-4-yl, 2-oxo-1,3-dioxolan-4-ylmethyl, 5-methyl-2-oxooxolan-5-yl and the like can be exemplified. . R ¹⁰ to R ¹³ of one or more carbon atoms is 2 to 15 of -CO ₂ - represents a monovalent hydrocarbon group containing a partial structure, the remains are each independently a hydrogen atom or a C 1 -C 15 straight chain, a branched or cyclic An alkyl group is shown. Having 2 to l5 of -CO ₂ - Examples of the monovalent hydrocarbon group containing a partial structure, specifically, 2-oxo-3-yloxy oxide solran Brassica Viterbo carbonyl, 4,4-dimethyl-2-oxo-3-oxide solran Iloxycarbonyl, 4-methyl-2-oxooxan-4-yloxycarbonyl, 2-oxo-1,3-dioxolan-4-ylmethyloxycarbonyl, 5-methyl-2-oxooxolane- 5-yloxycarbonyl etc. can be illustrated. Specifically as a C1-C15 linear, branched, cyclic alkyl group, the thing similar to what was illustrated by R <^3> can be illustrated. R ¹⁰ to R ¹³ may form a ring with each other, in which case at least one of R ¹⁰ to R ¹³ represents a divalent hydrocarbon group containing a C 1 -C 15 -CO ₂ -part structure, and the others are each independently A single bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms is shown. 1 to 15 carbon atoms of -CO ₂ - Examples of the divalent hydrocarbon group containing a partial structure, specifically, 1-oxo-2-oxa-propane-1,3-diyl, 1,3-dioxo-2-oxa-propane- In addition to 1,3-diyl, 1-oxo-2-oxabutane-1,4-diyl, 1,3-dioxo-2-oxabutane-1,4-diyl and the like, the -CO ₂ -partial structure is contained. The thing etc. which removed one hydrogen atom from what was illustrated by the monovalent hydrocarbon group mentioned above can be illustrated. As a C1-C15 linear, branched, cyclic alkylene group, what specifically removed one hydrogen atom from what was illustrated by R <^3> , etc. can be illustrated. R <^14> represents a C7-C5 polycyclic hydrocarbon group or the alkyl group containing a polycyclic hydrocarbon group, and specifically, norbornyl, bicyclo [3.3.1] nonyl, tricyclo [5.2.1.0 ^2,6 ] decyl , Adamantyl, ethyl adamantyl, butyl adamantyl, norbornylmethyl, adamantylmethyl and the like. R ¹⁵ represents an acid labile group. k is 0 or 1; a1, a2, a3, b1, b2, b3, c1, c2, c3, d1, d2, d3, e are numbers of 0 or more and less than 1, and a1 + a2 + a3 + b1 + b2 + b3 + c1 + c2 + c3 + d1 + d2 + d3 + e = 1 is satisfied.
Specifically as an acid labile group of R <^15> , the group represented by L1-L4 of following General formula (3), a C4-C20, Preferably the C4-C15 tertiary alkyl group, and each alkyl group are C1-C6 trialkylsilyl, respectively Group, a C4-C20 oxoalkyl group, etc. are mentioned.
In the above formula, R ^L01 , R ^L02 represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group, etc. can be illustrated. R ^L03 represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and a linear, branched, cyclic alkyl group, and some of these hydrogen atoms are hydroxyl, alkoxy And substituted groups, oxo groups, amino groups, alkylamino groups, and the like, and specifically the following substituted alkyl groups and the like can be exemplified:
.
R ^L01 and R ^L02 , R ^L01 and R ^L03 , R ^L02 and R ^L03 may form a ring, and when forming a ring, R ^L01 , R ^L02 and R ^L03 each have 1 to 18 carbon atoms, preferably 1 to 18 carbon atoms. 10 linear or branched alkylene groups are shown.
R ^L04 represents a C4-C20, preferably a C3- ^C15 tertiary alkyl group, each alkyl group each having a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or a group represented by the above formula L1, Specific examples of tertiary alkyl groups include tert-butyl, tert-amyl, 1,1-diethylpropyl, 1-ethylcyclopentyl, 1-butylcyclopentyl, 1-ethylcyclohexyl and 1-butyl Cyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, 2-methyl-2-adamantyl group, and the like. Specific examples of the trialkylsilyl group include trimethylsilyl. And triethylsilyl group, dimethyl-tert-butylsilyl group and the like. Specific examples of the oxoalkyl group include 3-oxocyclohexyl group, 4-methyl-2-oxooxan-4-yl group, and 5-methyl-. 5-oxo oxolan-4-yl group etc. are mentioned. a is an integer of 0-6.
R ^L05 represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an aryl group which may be substituted with 6 to 20 carbon atoms. Specific examples of the linear, branched and cyclic alkyl group include methyl, ethyl and propyl groups. , Isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclopentylethyl group , A cyclohexylmethyl group, a cyclohexylethyl group, etc. can be illustrated, As a aryl group which may be substituted, a phenyl group, methylphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, etc. can be illustrated specifically ,. m is 0 or 1, n is 0, 1, 2, 3, and is a number which satisfy | fills 2m + n = 2 or 3.
R ^L06 represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an aryl group which may be substituted with 6 to 20 carbon atoms, and specifically, the same as those for R ^L05 can be exemplified. R ^L07 to R ^L16 each independently represent a hydrogen atom or a monovalent hydrocarbon group which may include a hetero atom having 1 to 15 carbon atoms, and a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group , tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclopentyl Linear, branched, cyclic alkyl groups such as ethyl group, cyclopentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group and cyclohexylbutyl group, and some of these hydrogen atoms are hydroxyl group, alkoxy group, carboxyl group, alkoxycarbonyl group, oxo group, The thing substituted by an amino group, an alkylamino group, a cyano group, a mercapto group, an alkylthio group, a sulfo group etc. can be illustrated. R ^L07 to R ^L16 may form a ring with each other (for example, R ^L07 and R ^L08 , R ^L07 and R ^L09 , R ^L08 and R ^L10 , R ^L09 and R ^L10 , R ^L11 and R ^L12 , R ^L13 And R ^L14 ), in which case a divalent hydrocarbon group which may include a hetero atom having 1 to 15 carbon atoms, and one hydrogen atom removed from the one exemplified in the monovalent hydrocarbon group can be exemplified. . In addition, R ^L07 to R ^L16 may be bonded to adjacent carbons without intervening with each other to form a double bond (for example, R ^L07 and R ^L09 , R ^L09 and R ^L15 , R ^L13 and R ^L15 etc.).
Specific examples of the linear or branched group among the acid labile groups represented by L1 of the general formula (3) include the following groups.
Among the acid labile groups represented by L1 of the general formula (3), specifically, cyclic ones include tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, tetrahydropyran-2-yl group, and 2-methyltetra. Hydropyran-2-yl group etc. can be illustrated.
Specific examples of the acid labile group represented by L2 in the general formula (3) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group and 1,1-diethylpropyl Oxycarbonyl group, 1,1-diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-ethyl-2 -Cyclopentenyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group, etc. can be illustrated.
Specific examples of the acid labile group represented by L 3 of Formula 3 include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butylcyclopentyl, 1-sec-butylcyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl, 3-ethyl-1-cyclopenten-3-yl, 3-methyl- 1-cyclohexen-3-yl, 3-ethyl-1-cyclohexen-3-yl and the like can be exemplified.
As an acid labile group represented by L4 of the said General formula (3), the following group can be illustrated specifically ,.
Examples of the tertiary alkyl group, trialkylsilyl group and oxoalkyl group of the acid labile group of R ¹⁵ include those exemplified above.
In addition, the weight average molecular weight of the high molecular compound mix | blended with the resist material of this invention is 1,000-500,000, Preferably it is 3,000-100,000. If it is out of this range, etching resistance may fall extremely, or the dissolution rate difference before and after exposure may not be secured, and resolution may fall.
In addition, the said high molecular compound is not limited to 1 type, It can add 2 or more types. By using a plurality of high molecular compounds, the performance of the resist material can be adjusted.
In the resist material of the present invention, a compound different from the sulfonium salt represented by the formula (1) can be blended as an acid generator.
As a compound to mix as an acid generator,
i. An onium salt represented by P1a-1, P1a-2 of Formula 4 or P1b of Formula 5,
ii. A diazomethane derivative represented by P2 of the following formula (6),
iii. Glyoxime derivative represented by P3 of Formula 7,
iv. A bissulphone derivative represented by P4 of the following formula (8),
v. Sulfonic acid esters of N-hydroxyimide compounds represented by P5 of the following formula (9),
vi. β-ketosulfonic acid derivatives,
vii. Disulfone derivatives,
viii. Nitrobenzylsulfonate derivatives,
ix. Sulfonic acid ester derivatives;
^Wherein R ^101a , R ^101b and R ^101c each represent a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, an aryl group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms. An aralkyl group or an aryloxoalkyl group of 12, and some or all of the hydrogen atoms of these groups may be substituted by an alkoxy group or the like, and R ^101b and R ^101c may form a ring, and when forming a ring, R ^101b and R ^101c each represent an alkylene group having 1 to 6 carbon atoms, and K ⁻ represents a non-nucleophilic counter ion.
R ^101a , R ^101b , and R ^101c may be the same as or different from each other. Specifically, as an alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group , Hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, adamantyl group and the like. Examples of the alkenyl group include vinyl group, allyl group, propenyl group, butenyl group, hexenyl group, cyclohexenyl group and the like. 2-oxocyclopentyl group, 2-oxocyclohexyl group, etc. are mentioned as an oxoalkyl group, 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2- (4-methylcyclohexyl) -2-oxoethyl group etc. are mentioned. As an aryl group, alkoxy, such as a phenyl group, a naphthyl group, and a p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, an ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, etc. Alkyl naph, such as alkylphenyl groups, such as a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert- butylphenyl group, 4-butylphenyl group, and dimethylphenyl group, methylnaphthyl group, and ethyl naphthyl group, etc. Dialkoxy naphthyl groups, such as an alkoxy naphthyl group, such as a methyl group, a methoxy naphthyl group, and an ethoxy naphthyl group, a dimethyl naphthyl group, a diethyl naphthyl group, dialkoxy naphthyl groups, such as a dialkyl naphthyl group, a dimethoxy naphthyl group, and a diethoxy naphthyl group, etc. are mentioned. Can be. Examples of the aralkyl group include benzyl group, phenylethyl group and phenethyl group. As an aryl oxo alkyl group, 2-aryl-2-oxoethyl groups, such as a 2-phenyl- 2-oxo ethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group, etc. Etc. can be mentioned. Examples of non-nucleophilic counter ions of K ⁻ include halide ions such as chloride ions and bromide ions, triflate, fluoroalkylsulfonates such as 1,1,1-trifluoroethanesulfonate and nonafluorobutanesulfonate, and tosyl Alkyl sulfonates, such as aryl sulfonates, a mesylate, butane sulfonate, such as a late, a benzene sulfonate, 4-fluorobenzene sulfonate, a 1,2,3,4,5-pentafluorobenzene sulfonate, are mentioned. have.
In the above formula, R ^102a and R ^102b each represent a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R ¹⁰³ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and R ^104a And R ^104b each represent a 2-oxoalkyl group having 3 to 7 carbon atoms, and K ⁻ represents a non-nucleophilic counter ion.
Specific examples of the R ^102a and R ^102b include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl and cyclophene A methyl group, a cyclohexyl group, a cyclopropylmethyl group, 4-methylcyclohexyl group, a cyclohexylmethyl group, etc. are mentioned. ^Examples of R ¹⁰³ include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, 1,4-cyclohexylene group, 1,2-cyclohexylene group, 1 A, 3-cyclopentylene group, a 1, 4- cyclooctylene group, a 1, 4- cyclohexane dimethylene group, etc. are mentioned. ^{Examples of} R ^104a and R ^104b include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, a 2-oxocycloheptyl group, and the like. K ^- may be the same as described in the formulas P1a-1 and P1a-2.
In the above formula, R ¹⁰⁵ and R ¹⁰⁶ represent a linear, branched or cyclic alkyl or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.
^Examples of the alkyl group of R ¹⁰⁵ and R ¹⁰⁶ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, amyl group and cyclo A pentyl group, a cyclohexyl group, a cycloheptyl group, a norbornyl group, an adamantyl group etc. are mentioned. Examples of the halogenated alkyl group include trifluoromethyl group, 1,1,1-trifluoroethyl group, 1,1,1-trichloroethyl group, and nonafluorobutyl group. As an aryl group, alkoxyphenyl groups, such as a phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, and m-tert-butoxyphenyl group, 2-methylphenyl Alkylphenyl groups, such as group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert- butylphenyl group, 4-butylphenyl group, and a dimethylphenyl group, are mentioned. Examples of the halogenated aryl group include a fluorophenyl group, a chlorophenyl group, 1,2,3,4,5-pentafluorophenyl group, and the like. As an aralkyl group, a benzyl group, a phenethyl group, etc. are mentioned.
Wherein R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are linear, branched or cyclic alkyl or halogenated alkyl groups having 1 to 12 carbon atoms, aryl or halogenated aryl groups having 6 to 20 carbon atoms, or aralkyl having 7 to 12 carbon atoms. Group, R ¹⁰⁸ and R ¹⁰⁹ may be bonded to each other to form a cyclic structure, and when forming a cyclic structure, R ¹⁰⁸ and R ¹⁰⁹ each represent a linear or branched alkylene group having 1 to 6 carbon atoms.
Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group, and aralkyl group for R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ include the same groups as described for R ¹⁰⁵ and R ¹⁰⁶ . Also, R ^108, R ¹⁰⁹ of the alkylene group may be mentioned methylene group, ethylene group, propylene group, butylene group, hexylene group and the like.
In the above formula, R ^101a and R ^101b are the same as above.
In the above formula, R ¹¹⁰ represents an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms, and some or all of the hydrogen atoms of these groups are further linearly having 1 to 4 carbon atoms. Or a branched alkyl group or alkoxy group, nitro group, acetyl group, or phenyl group, R ¹¹¹ is a linear, branched or substituted alkyl group, alkenyl group or alkoxyalkyl group, phenyl group having 1 to 8 carbon atoms, or A naphthyl group, and some or all of the hydrogen atoms in these groups are more preferably an alkyl or alkoxy group having 1 to 4 carbon atoms; Phenyl group which may be substituted by the C1-C4 alkyl group, an alkoxy group, a nitro group, or an acetyl group; Hetero aromatic groups having 3 to 5 carbon atoms; Or a chlorine atom or a fluorine atom.
Here, as the arylene group of R ¹¹⁰ , a 1,2-phenylene group, a 1,8-naphthylene group, and the like, and as an alkylene group, a methylene group, a 1,2-ethylene group, a 1,3-propylene group, 1,4-butyl As an alkenylene group, a 1, 2- vinylene group, a 1-phenyl- 1, 2- vinylene group, 5- is a benzene group, a 1-phenyl- 1, 2- ethylene group, a norbornane-2, 3-diyl group, etc. Norbornene-2,3-diyl group etc. are mentioned. ^Examples of the alkyl group of R ¹¹¹ are the same as those of R ^101a to R ^{101c. Examples} of the alkenyl group include a vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, isofurenyl group, 1-pentenyl group, and 3-pente. A nilyl group, 4-pentenyl group, dimethylallyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group, 7-octenyl group, etc. As the alkoxyalkyl group, methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, pentyloxymethyl group, hexyloxymethyl group, heptyloxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, pentyloxy Ethyl group, hexyloxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, methoxypentyl group, ethoxypentyl group , Methoxyhexyl group, methoxyheptyl group and the like.
In addition, examples of the alkyl group having 1 to 4 carbon atoms which may be further substituted include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and the like. A phenyl group which may be substituted with an alkyl group, an alkoxy group, a nitro group, or an acetyl group having 1 to 4 carbon atoms, such as a period, an ethoxy group, a propoxy group, an isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, etc. Examples of the phenyl group, tolyl group, p-tert-butoxyphenyl group, p-acetylphenyl group, p-nitrophenyl group and the like include pyridyl group, furyl group and the like as the hetero aromatic group having 3 to 5 carbon atoms.
Specifically, for example, trifluoromethanesulfonic acid diphenyl iodonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyl iodonium, p-toluenesulfonic acid diphenyliodium, p-toluenesulfonic acid (p- tert-butoxyphenyl) phenyl iodonium, trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid bis (p-tert- Butoxyphenyl) phenylsulfonium, trifluoromethanesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenyl Sulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, nonafluorobutanesulfonic acid triphenylsulfonium, butanesulfonic acid Triphenylsulfonium, trifluoromethanesulfonic acid trimethylsulfonium, p-toluenesulfonic acid trimethylsulphate , Trifluoromethanesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) sulfonium, p-toluenesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) sulfonium, trifluoromethanesulfonic acid dimethylphenylsulfonium, p-toluene Sulfonic acid dimethylphenylsulfonium, trifluoromethanesulfonic acid dicyclohexylphenylsulfonium, p-toluenesulfonic acid dicyclohexylphenylsulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethanesulfonic acid cyclohexylmethyl (2- Oxocyclohexyl) sulfonium, trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium, ethylenebis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate], Onium salts such as 1,2'-naphthylcarbonylmethyl tetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) Diazomethane, bis (cyclohex) Sulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) dia Crude methane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane, Bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl Diazomethane such as diazomethane, 1-cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, and 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane Derivatives, bis-0- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-0- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-0- (p-toluenesulfonyl) -α-dicyclohexylglyoxime, bis-O- (p-toluenesulfonyl) -2,3-pentanedioneglyox Shim, bis-O- (p-toluenesulfonyl) -2-methyl-3,4-pentanedioneglyoxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bis-O- ( n-butanesulfonyl) -α-diphenylglyoxime, bis-O- (n-butanesulfonyl) -α-dicyclohexylglyoxime, bis-O- (n-butanesulfonyl) -2,3- Pentanedionoglyoxime, bis-O- (n-butanesulfonyl) -2-methyl-3,4-pentanedioneglyoxime, bis-0- (methanesulfonyl) -α-dimethylglyoxime, bis-0- (Trifluoromethanesulfonyl) -α-dimethylglyoxime, bis-0- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-O- (tert-butanesulfonyl ) -α-dimethylglyoxime, bis-0- (perfluorooctanesulfonyl) -α-dimethylglyoxime, bis-0- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-0- (benzene Sulfonyl) -α-dimethylglyoxime, bis-0- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-tert-butylbenzenesulfonyl) -α-dimethylglyoxime , Bis-0- (xylenesulfonyl) -α-dimethylglycol Glyoxime derivatives such as lyoxime and bis-0- (camphorsulfonyl) -α-dimethylglyoxime, bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane , Bissulfon derivatives such as bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane and bisbenzenesulfonylmethane, 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) Β-ketosulfone derivatives such as propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane, disulfone derivatives such as diphenyldisulfone and dicyclohexyl disulfone, p-toluenesulfonic acid 2,6 -Nitrobenzylsulfonate derivatives such as dinitrobenzyl and p-toluenesulfonic acid 2,4-dinitrobenzyl, 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoro Sulfonic acid ester derivatives such as methanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene, and N-hydroxysuccinimide De-methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide ethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide 1-octanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxysuccinate Imide p-methoxybenzenesulfonic acid ester, N-hydroxysuccinimide 2-chloroethanesulfonic acid ester, N-hydroxysuccinimide benzenesulfonic acid ester, N-hydroxysuccinimide 2,4,6-trimethylbenzene Sulfonic acid ester, N-hydroxysuccinimide 1-naphthalenesulfonic acid ester, N-hydroxysuccinimide 2-naphthalenesulfonic acid ester, N-hydroxy-2-phenylsuccinimide methanesulfonic acid ester, N-hydroxymaleimide Methanesulfonic acid ester, N-hydroxymaleimide ethanesulfonic acid ester, N-hydroxy-2-phenylmaleimide methanesulfonic acid ester, N-hydroxyglutalimide methanesulfonic acid ester, N-hydroxyglutalimide benzenesulfonic acid Ester, N-hydroxyphthalimide methanesulfonic acid ester, N-hydroxyphthalimide benzenesulfonic acid ester, N-hydroxyphthalimide trifluoromethanesulfonic acid ester, N-hydroxyphthalimide p-toluenesulfonic acid ester , N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimide benzenesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboxyimide methanesulfonic acid ester, N-hydroxy N-hydrides such as oxy-5-norbornene-2,3-dicarboxyimide trifluoromethanesulfonic acid ester and N-hydroxy-5-norbornene-2,3-dicarboxyimide p-toluenesulfonic acid ester Roxy The sulfonic acid ester derivative of a mid compound, etc. are mentioned, but trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, and trifluoromethanesulfonic acid tris (p- tert-butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) Sulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethanesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) sulfonium, trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl Onium salts such as sulfonium, 1,2'-naphthylcarbonylmethyl tetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis ( Cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis ( Sobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsul Diazomethane derivatives such as fonyl) diazomethane, bis-0- (p-toluenesulfonyl) -α-dimethylglyoxime, and bis-O- (n-butanesulfonyl) -α-dimethylglyoxime Oxime derivatives, bissulfone derivatives such as bisnaphthylsulfonylmethane, N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid Ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methane N-hydroxy, such as sulfonic acid ester and N-hydroxy naphthalimide benzene sulfonic acid ester It is already in use as a sulfonic acid ester derivative of the imide compound preferred. In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more type. Since the onium salt is excellent in spherical formation improvement effect, and the diazomethane derivative and glyoxime derivative are excellent in standing wave reduction effect, fine adjustment of a profile can be performed by combining both.
The addition amount of the acid generator is a total amount with the sulfonium salt of the formula (1), preferably 0.1 to 15 parts, more preferably 0.5 to 8 parts relative to 100 parts of the base resin. When less than 0.1 part, it will become a reduction degree, and when more than 15 parts, transparency may fall and the resolution performance of a resist material may fall.
The organic solvent used in the present invention may be any organic solvent which can dissolve a base resin, an acid generator, and other additives. As such an organic solvent, for example, ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1- Alcohols such as ethoxy-2-propanol, ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether and diethylene glycol dimethyl ether; Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono esters such as tert-butyl ether acetate, and the like, and may be used alone or in combination of two or more thereof. Although it is possible, it is not limited to these. In the present invention, among these organic solvents, in addition to diethylene glycol dimethyl ether and 1-ethoxy-2-propanol, which are excellent in solubility of the acid generator in the resist component, propylene glycol monomethyl ether acetate as a safety solvent and a mixed solvent thereof are preferably used. Used.
The amount of the organic solvent to be used is preferably 200 to 1,000 parts, particularly 400 to 800 parts, based on 100 parts of the base resin.
The dissolution control agent can be further added to the resist material of the present invention. As a dissolution control agent, the average molecular weight is 100-1,000, Preferably it is 150-800, At the same time, the hydrogen atom of this phenolic hydroxyl group of the compound which has 2 or more of phenolic hydroxyl groups in a molecule | numerator is averaged 0-100 as a whole by acid labile group. The compound which substituted the hydrogen atom of this carboxy group of the compound which has a carboxy group in a molecule | numerator or a molecule | numerator by the acid labile group in the ratio of an average of 80-100 mol% as a whole is mix | blended.
In addition, the substitution rate by the acid labile group of the hydrogen atom of a phenolic hydroxyl group or a carboxyl group is 0 mol% or more, Preferably it is 30 mol% or more of the whole phenolic hydroxyl group or carboxyl group, The upper limit is 100 mol%, More preferably, It is 80 mol%.
In this case, as a compound which has two or more such phenolic hydroxyl groups, or a compound which has a carboxyl group, what is represented by D1-D14 of following General formula (10) is preferable.
Provided that R ²⁰¹ and R ²⁰² each represent a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, and R ²⁰³ represents a hydrogen atom or a straight or branched carbon group having 1 to 8 carbon atoms Alkyl group or alkenyl group or-(R ²⁰⁷ ) _h COOH, R ²⁰⁴ is-(CH ₂ ) i- (i = 2 to 10), arylene group having 6 to 10 carbon atoms, carbonyl group, sulfonyl group, oxygen atom Or a sulfur atom, R ²⁰⁵ represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom, or a sulfur atom, and R ²⁰⁶ represents a hydrogen atom, a carbon group having 1 to 8 carbon atoms A linear or branched alkyl group, an alkenyl group, or a phenyl group or a naphthyl group substituted with a hydroxyl group, respectively, R ²⁰⁷ represents a linear or branched alkylene group having 1 to 10 carbon atoms, and R ²⁰⁸ represents a hydrogen atom or a hydroxyl group J is 0 Is an integer of 5 to 5, u and h are 0 or 1, and s, t, s', t ', s'', t '' are s + t = 8, s' + t '= 5, s', respectively. It is a number which satisfy | fills "+ t" = 4, and simultaneously has one or more hydroxyl groups in each phenyl skeleton, and (alpha) is a number which makes the molecular weight of the compound represented by D8, D9 of the said Formula (10) into 100-1,000.
In the above formula, as R ²⁰¹ , R ²⁰² , for example, a hydrogen atom, a methyl group, an ethyl group, a butyl group, a propyl group, an ethynyl group, a cyclohexyl group, and as R ^203, for example, the same as R ²⁰¹ , R ²⁰² , or- As COOH, -CH ₂ COOH, R ^204, for example, an ethylene group, a phenylene group, a carbonyl group, a sulfonyl group, an oxygen atom, a sulfur atom, etc., as R ^205, for example, the same as a methylene group or R ^204, and as R ^206, for example Examples thereof include a hydrogen atom, a methyl group, an ethyl group, a butyl group, a propyl group, an ethynyl group, a cyclohexyl group, a phenyl group substituted with a hydroxyl group, and a naphthyl group.
Here, as an acid labile group of a dissolution control agent, the group represented by L1-L4 of the said General formula (3), a C4-C20 tertiary alkyl group, the C1-C6 trialkylsilyl group, C4-C20 of each alkyl group, respectively And oxoalkyl groups.
<Formula 3>
In the above formula, the definitions and specific examples of R ^L01 to R ^L16 , a, m, and n are the same as above.
The compounding quantity of the said dissolution control agent is 0-50 parts with respect to 100 parts of base resin, Preferably it is 5-50 parts, More preferably, it is 10-30 parts, It can use individually or in mixture of 2 or more types. If the blending amount is less than 5 parts, there is no improvement in resolution, while if it is more than 50 parts, film reduction of the pattern may occur and the resolution may decrease.
In addition, such dissolution control agents are synthesized by introducing an acid labile group using an organic chemical formulation to a compound having a phenolic hydroxyl group or a carboxyl group.
In addition, a basic compound can be mix | blended with the resist material of this invention.
As a basic compound, the compound which can suppress the diffusion rate at the time when the acid which generate | occur | produces with an acid generator in a resist film is suitable. By compounding a basic compound, the diffusion rate of an acid in a resist film is suppressed, the resolution is improved, the change in sensitivity after exposure can be suppressed, or the exposure margin, pattern profile, etc. can be improved by making the base or environment dependent less.
As such a basic compound, primary, secondary and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, and nitrogen-containing compounds having a hydroxyl group , A nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative, and the like.
Specifically, as the primary aliphatic amines, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert -Amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like are exemplified, and As secondary aliphatic amines, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclo Pentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylene Diamine, N, N-dimethyltetraethylenepentamine, and the like are exemplified; As the aliphatic amines, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, Trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ', N'-tetramethylmethylenediamine, N , N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyltetraethylenepentamine and the like.
In addition, examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine, and the like. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (for example, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-di Nitroaniline, N, N-dimethyltoluidine, etc.), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g. pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (e.g., oxazole, isoxazole, etc.), thiazole derivatives (For example, thiazole, isothiazole, etc.), imidazole derivatives (for example, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), Lazole derivatives, furazane derivatives, pyrroline derivatives (e.g. pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (e.g. pyrrolidine, N-methylpyrrolidine, pyrrolidinone , N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g. pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine , Dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1 -Methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives , Pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, Lepoline derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indolin derivatives, quinoline derivatives (e.g. quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinox Saline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthrizine derivatives, acridine derivatives, phenadine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine Derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.
In addition, examples of the nitrogen-containing compound having a carboxyl group include aminobenzoic acid, indolecarboxylic acid, and amino acid derivatives (for example, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylosin, leucine, Methylonine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine), and the like, and examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridine sulfonic acid and p-toluene sulfonic acid pyridinium. Illustrative examples of the nitrogen-containing compound having a hydroxyl group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemethanol hydrate, and monoethanolamine. , Diethanolamine, triethanolamine, N-ethyl diethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-imino diethanol, 2-amino Tanol, 3-amino-1-propanol, 4-amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) Piperazine, 1- [2- (2-hydroxyethoxy) ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2 -Pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyurorizine, 3-quinuclidinol, 3-tropanol, 1 -Methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, etc. are illustrated. Examples of the amide derivatives include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like. Phthalimide, succinimide, maleimide, etc. are illustrated as an imide derivative.
Moreover, you may mix | blend the basic compound represented by B1 and B2 of following formula (11).
Wherein R ³⁰¹ , R ³⁰² , R ³⁰³ , R ³⁰⁷ and R ³⁰⁸ are each independently a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, R ³⁰⁴ , R ³⁰⁵ , R ³⁰⁶ , R ³⁰⁹ , R ³¹⁰ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an amino group, and R ³⁰⁴ and R ³⁰⁵ , R ³⁰⁴ and R ³⁰⁶ , R ³⁰⁵ and R ³⁰⁷ , R ³⁰⁴ and R ³⁰⁵ and R ³⁰⁶ , and R ³⁰⁹ and R ³¹⁰ are respectively May combine to form a ring, wherein S, T and U are each an integer of 0 to 20, provided that S ³⁰⁴ , R ³⁰⁵ , R ³⁰⁶ , R ³⁰⁹ , and R ³¹⁰ are hydrogen atoms when S, T, and U = 0. Does not include
Herein, the alkylene groups of R ³⁰¹ , R ³⁰² , R ³⁰³ , R ³⁰⁷ and R ^{308 have} 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, specifically methylene and ethylene groups. , n-propylene group, isopropylene group, n-butylene group, isobutylene group, n-pentylene group, isopentylene group, hexylene group, nonylene group, decylene group, cyclopentylene group, cyclohexylene group and the like Can be.
Also, R ^304, R ^305, R ^306, R ^309, examples of the alkyl group of R ³¹⁰ to having 1 to 20 carbon atoms, preferably 1 to 8, more preferably 1 to 6, all of which are straight, branched, cyclic of It can be either. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, hexyl group, nonyl group, decyl group and dodecyl group , Tridecyl group, cyclopentyl group, cyclohexyl group and the like.
In addition, when R ³⁰⁴ and R ³⁰⁵ , R ³⁰⁴ and R ³⁰⁶ , R ³⁰⁵ and R ³⁰⁶ , R ³⁰⁴ and R ³⁰⁵ and R ³⁰⁶ , R ³⁰⁹ and R ³¹⁰ form a ring, the carbon number of the ring is 1 to 20, Preferably it is 1-8, More preferably, it is 1-6, Moreover, these rings may have the C1-C6, especially 1-4 alkyl group branched.
S, T and U are each an integer of 0-20, More preferably, it is an integer of 1-10, More preferably, it is an integer of 1-8.
Specific examples of the compound represented by B1 and B2 of the above formula (11) include tris {2- (methoxymethoxy) ethyl} amine, tris {2- (methoxyethoxy) ethyl} amine, and tris [2-{( 2-methoxyethoxy) methoxy} ethyl] amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, tris [2-{(2-hydroxyethoxy) ethoxy} ethyl] amine, 4, 7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.8] hexacoic acid, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5 ] Eicoic acid, 1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18 -Crown-6 and the like. Tertiary amines, aniline derivatives, pyrrolidine derivatives, pyridine derivatives, quinoline derivatives, amino acid derivatives, nitrogen-containing compounds with hydroxyl groups, nitrogen-containing compounds with hydroxyphenyl groups, alcohol-containing nitrogen compounds, amide derivatives, imide derivatives , Tris {2- (methoxymethoxy) ethyl} amine, tris {(2- (2-methoxyethoxy) ethyl} amine, tris [2-{(2-methoxyethoxy) methyl} ethyl] amine , 1-aza-15-crown-5 and the like are preferred.
The compounding quantity of the said basic compound is 0.001-10 parts with respect to 1 part of acid generators, Preferably it is 0.01-1 part. When the compounding quantity is less than 0.001 part, the effect as an additive may not be fully acquired, and when it exceeds 10 parts, resolution and a sensitivity may fall.
In addition, a compound having a group represented by ≡C-COOH in the molecule can be blended into the resist material of the present invention.
As a compound which has group represented by -C-COOH in a molecule | numerator, 1 type (s) or 2 or more types of compounds chosen from the following group I and II can be used, for example, It is not limited to these. By combining this component, the PED stability of the resist is improved, and the edge raffnes on the nitride film base are improved.
[Group I]
Some or all of the hydrogen atoms of the phenolic hydroxyl groups of the compounds represented by formulas A1 to A10 are substituted by -R ⁴⁰¹ -COOH (R ⁴⁰¹ is a linear or branched alkylene group having 1 to 10 carbon atoms); And at the same time the molar ratio between the phenolic hydroxyl group (C) in the molecule and the group (D) represented by ≡C-COOH is C / (C + D) = 0.1 to 1.0.
[Group II]
A compound represented by A1 to A10 of Formula 12 and A11 to A15 of Formula 14;
In the above formula, R ⁴⁰⁸ represents a hydrogen atom or a methyl group, R ⁴⁰² , R ⁴⁰³ represents a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, respectively, and R ⁴⁰⁴ represents a hydrogen atom or carbon number A linear or branched alkyl or alkenyl group of 1 to 8, or a-(R ⁴⁰⁹ ) _h -COOR 'group (R' represents a hydrogen atom or -R ⁴⁰⁹ -COOH), and R ⁴⁰⁵ represents-(CH ₂ ) _i- (i = 2 to 10), an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, R ⁴⁰⁶ is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, A carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, R ⁴⁰⁷ represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, an alkenyl group, a phenyl group or a naphthyl group each substituted with a hydroxyl group, and R ⁴⁰⁹ is Straight or minute carbon atoms of 1 to 10 Represents an alkylene group on the, R ⁴¹⁰ is a represents a hydrogen atom or a group having 1 to 8 carbon atoms in a straight or branched alkyl or alkenyl group or a -R ⁴¹¹ -COOH, R ⁴¹¹ is a straight or branched having 1 to 10 carbon atoms ground An alkylene group, j is an integer from 0 to 5, u, h is 0 or 1, and s1, t1, s2, t2, s3, t3, s4, t4 are each s1 + t1 = 8, s2 + t2 = 5, s3 + t3 = 4, s4 + t4 = 6, and at the same time, a number having at least one hydroxyl group in each phenyl skeleton, κ is a number having a weight average molecular weight of 1,000 to 5,000 as a compound represented by A6 of formula (12) And (lambda) is a number which makes the compound represented by A7 of General formula (12) a weight average molecular weight 1,000-10,000.
In the above formula, R ⁴⁰² , R ⁴⁰³ , R ⁴¹¹ represent the same meaning as above, R ⁴¹² represents a hydrogen atom or a hydroxyl group, s5, t5 is s5≥0, t5≥0 and satisfies s5 + t5 = 5. And h 'is 0 or 1.
Specific examples of the present component include, but are not limited to, compounds represented by AI-1 to L4 of Formula 14 and AII-1 to 10 of Formula 15.
In the above formula, R '' represents a hydrogen atom or a CH ₂ COOH group, and in each compound, 10 to 100 mol% of R '' is a CH ₂ COOH group, and α, κ represents the same meaning as above.
In addition, the compound which has group represented by -C-COOH in the said molecule can be used individually by 1 type or in combination of 2 or more types.
The amount of the compound having a group represented by ≡C-COOH in the molecule is 0 to 5 parts, preferably 0.1 to 5 parts, more preferably 0.1 to 3 parts, even more preferably 0.1 to 100 parts of the base resin. To 2 parts. When more than 5 parts, the resolution of a resist material may fall.
Moreover, an acetylene alcohol derivative can be mix | blended with the resist material of this invention as an additive, and, thereby, storage stability can be improved.
As an acetylene alcohol derivative, what is represented by S1 and S2 of following formula (16) can be used preferably.
In the above formula, R ⁵⁰¹ , R ⁵⁰² , R ⁵⁰³ , R ⁵⁰⁴ , R ⁵⁰⁵ each represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, X, Y represents 0 or a positive number, The values 0 ≦ X ≦ 30, 0 ≦ Y ≦ 30, and 0 ≦ X + Y ≦ 40 are satisfied.
As the acetylene alcohol derivative, preferably, quinolin 61, sufinol 82, sufinol 104, sufinol 104E, sufinol 104H, sufinol 104A, sufinol TG, sufinol PC, sufinol 440, sufinol 465, sufinol 485 (Air Products and Chemicals (made by Air Products and Chemicals Inc.), Sufinol El004 (made by Nisshin Chemical Industries, Ltd.), etc. are mentioned.
The amount of the acetylene alcohol derivative added is 0.01 to 2% by weight, more preferably 0.02 to 1% by weight in 100% by weight of the resist composition. When less than 0.01 weight%, the effect of improving coating property and storage stability may not be fully acquired, and when more than 2 weight%, the resolution of a resist material may fall.
To the resist material of this invention, surfactant commonly used in order to improve applicability as an arbitrary component other than the said component can be added. In addition, the addition amount of an arbitrary component can be made into the normal amount in the range which does not impair the effect of this invention.
As the surfactant, nonionic ones are preferable, and perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkylamine oxides, perfluoroalkyl EO adducts, fluorine-containing organosiloxane compounds, and the like can be given. Can be. For example, Flowride "FC-430", "FC-431" (all are manufactured by Sumitomo 3M Co., Ltd.), Supron "S-141", "S-145" (all are manufactured by Asahi Glass Co., Ltd.) , United "DS-401", "DS-403", "DS-451" (all manufactured by Daikin Kogyo Co., Ltd.), "MegaPeck" F-8151 "(manufactured by Dainippon Ink Kogyo Co., Ltd.), "X-70-092", "X-70-093" (all manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Preferably, the flowride "FC-430" (Sumitomo 3M Co., Ltd.) is mentioned. ) And "X-70-093" (made by Shin-Etsu Chemical Co., Ltd.).
In order to form a pattern using the resist material of the present invention, a well-known lithography technique can be employed, for example, so as to have a film thickness of 0.3 to 2.0 탆 on a substrate such as a silicon wafer by spin coating or the like. It is applied and it is prebaked on a hot plate for 1 to 10 minutes at 60 to 150 ° C., preferably at 80 to 130 ° C. for 1 to 5 minutes. Subsequently, a mask for forming a desired pattern is covered on the resist film, and the ArF excimer laser is irradiated to an exposure dose of about 1 to 100 mJ / cm ² , preferably about 5 to 50 mJ / cm ² , and then a hot plate. Post exposure bake (PEB) at 60 to 150 ° C. for 1 to 5 minutes, preferably at 80 to l30 ° C. for 1 to 3 minutes. Further, the dip method is performed for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, using a developing solution of an aqueous alkali solution such as tetramethylammonium hydroxide (TMAH) at 0.1 to 5%, preferably 2 to 3%. By developing by conventional methods, such as a puddle method and the spray method, the desired pattern is formed on a base. In addition, when the said range is out of an upper limit and a lower limit, a desired pattern may not be obtained.
Hereinafter, although an Example and a comparative example are given and this invention is concretely demonstrated, this invention is not limited to the following Example.
<Example>
The sulfonium salts (PAG 1 to 8) represented by the following formula (17) were evaluated for sensitivity and resolution when used as a resist.
<Examples 1 to 40> Resolution evaluation of resist
A dissolution control agent represented by the following formula (19) using a sulfonium salt (PAG 1 to 8) represented by the above formula (17) as an acid generator and a polymer (polymer 1 to 8) represented by the following formula (18) as a base resin FC-430 (manufactured by Sumitomo 3M) with a composition shown in the table (DRR 1 to 4), a basic compound and a compound having a group represented by ≡C-COOH in a molecule represented by the following formula (20): 0.05 The resist liquids were each prepared by dissolving in a solvent containing% by weight to combine the resist materials and further filtering each composition with a 0.2 μm Teflon filter.

The resist solution was spin coated onto a silicon wafer and applied to a thickness of 0.5 μm. This silicon wafer was then baked at 110 ° C. for 90 seconds using a hot plate. This was exposed using an ArF excimer laser exposure apparatus (manufactured by Ristech Tech Japan) and an ArF excimer laser stepper (manufactured by Nikon Corporation, NA = 0.55), followed by baking (PEB) at 110 ° C. for 90 seconds (PEB) to obtain 2.38% of tetramethylammonium hydroxide. It was developed with an aqueous solution of seeds.
Evaluation of the resist was performed on the following items. First, sensitivity (Eth, mJ / cm ² ) was obtained. Subsequently, the exposure dose for resolving 0.25 μm line and space at 1: 1 is the optimum exposure dose (Eop, mJ / cm ² ), and the minimum line width (μm) of the line and space separated at this exposure dose is determined as the resolution of the evaluation resist. It was. The shape of the resolved resist pattern was observed using a scanning electron microscope. The sensitivity was evaluated for all resists using an ArF excimer laser exposure apparatus, and the resolution was evaluated for some resists using an ArF excimer laser stepper.
The composition and evaluation result of each resist are shown in Table 1 and Table 2. In addition, in Table 1 and Table 2, a solvent and a basic compound are as follows.
PGMEA: Propylene Glycol Methyl Ether Acetate
CyHO: cyclohexanone
PG / EL: Mixed solvent of 70% PGMEA and 30% ethyl lactate
TBA: tributylamine
TEA: Triethanolamine
TMMEA: Trismethoxymethoxyethylamine
TMEMEA: Trismethoxyethoxymethoxyethylamine
<Comparative Example>
For comparison, the sulfonium salts represented by the following formula (21) (PAG 9 to 16) were evaluated for sensitivity and resolution when used as a resist.
<Comparative Examples 1 to 8>
Using a sulfonium salt (PAG 9 to 16) represented by the formula (21), a resist was prepared in the composition shown in the table in the same manner as above, and the sensitivity and resolution were evaluated in the same manner as above.
The composition and evaluation result of each resist are shown in Table 3.
From the results of Tables 1 to 3, it was confirmed that the resist material of the present invention had high sensitivity and high resolution as compared with the conventional product.
ExampleSuzyAcid generatorDissolution control agentBasic compoundsolventSensitivityresolutionshape OnePolymer 1 (80)PAG 1 (1) TBA (0.10)PGMEA (480)3.20.18Rectangle 2Polymer 1 (80)PAG 2 (1) TBA (0.10)PGMEA (480)3.4-- 3Polymer 1 (80)PAG 3 (1) TBA (0.10)PGMEA (480)3.20.18Rectangle 4Polymer 1 (80)PAG 4 (1) TBA (0.10)PGMEA (480)3.2-- 5Polymer 1 (80)PAG 5 (1) TBA (0.10)PGMEA (480)5.00.18Rectangle 6Polymer 1 (80)PAG 6 (1) TBA (0.10)PGMEA (480)5.4-- 7Polymer 1 (80)PAG 7 (1) TBA (0.10)PGMEA (480)4.90.18Rectangle 8Polymer 1 (80)PAG 8 (1) TBA (0.10)PGMEA (480)5.1-- 9Polymer 1 (80)PAG 2 (1) TBA (0.10)CyHO (560)3.40.18Rectangle 10Polymer 2 (80)PAG 2 (1) TBA (0.10)CyHO (560)4.0-- 11Polymer 3 (80)PAG 2 (1) TBA (0.10)CyHO (560)3.10.18Rectangle 12Polymer 4 (80)PAG 2 (1) TBA (0.10)CyHO (560)3.7-- 13Polymer 5 (80)PAG 2 (1) TBA (0.10)CyHO (560)3.30.18Rectangle 14Polymer 6 (80)PAG 2 (1) TBA (0.10)CyHO (560)3.4-- 15Polymer 7 (80)PAG 2 (1) TBA (0.10)CyHO (560)3.20.18Rectangle 16Polymer 8 (80)PAG 2 (1) TBA (0.10)CyHO (560)3.4-- 17Polymer 3 (80)PAG 3 (1) TBA (0.10)CyHO (560)3.0-- 18Polymer 3 (80)PAG 3 (1) TEA (0.10)CyHO (560)3.3-- 19Polymer 3 (80)PAG 3 (1) TMMEA (0.10)CyHO (560)2.9-- 20Polymer 3 (80)PAG 3 (1) TMEMEA (0.10)CyHO (560)2.8-- 21Polymer 5 (80)PAG 4 (1) TEA (0.10)PG / EL (480)3.3-- 22Polymer 5 (80)PAG 4 (1)DRR 1 (16)TEA (0.10)PG / EL (480)3.0--
ExampleSuzyAcid generatorDissolution control agentBasic compoundsolventSensitivityresolutionshape 23Polymer 5 (64)PAG 4 (1)DRR 2 (16)TEA (0.10)PG / EL (480)3.1-- 24Polymer 5 (64)PAG 4 (1)DRR 3 (16)TEA (0.10)PG / EL (480)3.7-- 25Polymer 5 (64)PAG 4 (1)DRR 4 (16)TEA (0.10)PG / EL (480)3.2-26Polymer 7 (80)PAG 3 (1) TEA (0.10)CyHO (560)3.1-- 27Polymer 7 (64)PAG 3 (1)DRR 1 (16)TEA (0.10)CyHO (560)2.9-- 28Polymer 7 (64)PAG 3 (1)DRR 2 (16)TEA (0.10)CyHO (560)2.9-- 29Polymer 7 (64)PAG 3 (1)DRR 3 (16)TEA (0.10)CyHO (560)3.5-- 30Polymer 7 (64)PAG 3 (1)DRR 4 (16)TEA (0.10)CyHO (560)3.0-- 31Polymer 4 (80)PAG 5 (1) TEA (0.10)CyHO (560)5.4-- 32Polymer 4 (80)PAG 5 (1)ACC 1 (2)TEA (0.10)CyHO (560)5.3-- 33Polymer 4 (80)PAG 5 (1)ACC 2 (2)TEA (0.10)CyHO (560)5.5-- 34Polymer 8 (80)PAG 6 (1) TEA (0.10)PGMEA (480)5.3-- 35Polymer 8 (80)PAG 6 (1)ACC 1 (2)TEA (0.10)PGMEA (480)5.3-- 36Polymer 8 (80)PAG 6 (1)ACC 2 (2)TEA (0.10)PGMEA (480)5.4-- 37Polymer 3 (40) Polymer 5 (40)PAG 1 (1) TEA (0.10)PG / EL (480)3.1-- 38Polymer 3 (40) Polymer 5 (40)PAG 3 (1) TEA (0.10)PG / EL (480)3.2-- 39Polymer 5 (40) Polymer 7 (40)PAG 1 (1) TEA (0.10)CyHO (560)3.2-- 40Polymer 5 (40) Polymer 7 (40)PAG 3 (1) TEA (0.10)CyHO (560)3.2--
ExampleSuzyAcid generatorDissolution control agentBasic compoundsolventSensitivityresolutionshape OnePolymer 1 (80)PAG 9 (1) TBA (0.10)PGMEA (480)9.10.18Rectangle 2Polymer 1 (80)PAG 10 (1) TBA (0.10)PGMEA (480)9.9-- 3Polymer 1 (80)PAG 11 (1) TBA (0.10)PGMEA (480)9.00.18Rectangle 4Polymer 1 (80)PAG 12 (1) TBA (0.10)PGMEA (480)9.4-- 5Polymer 1 (80)PAG 13 (1) TBA (0.10)PGMEA (480)8.90.20Slightly tapered taper 6Polymer 1 (80)PAG 14 (1) TBA (0.10)PGMEA (480)9.2-- 7Polymer 1 (80)PAG 15 (1) TBA (0.10)PGMEA (480)8.50.20Slightly taper 8Polymer 1 (80)PAG 16 (1) TBA (0.10)PGMEA (480)9.2--
Since the resist material of the present invention is sensitive to ArF excimer laser light and has excellent sensitivity, resolution, and thickness, it is advantageous for etching, and thus it is possible to easily form a fine and vertical pattern with respect to the substrate. Have

权利要求:
Claims (3)
[1" claim-type="Currently amended] A resist material for an ArF excimer laser, comprising a base resin, an acid generator, and a solvent, wherein the acid generator is a sulfonium salt represented by the following general formula (1).
<Formula 1>

Where
R ¹ represents a hydroxyl group, a nitro group, or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 15 carbon atoms which may contain O, N or S atoms, and two R ¹ may form a ring. In that case, R ¹ represents a linear, branched or cyclic divalent hydrocarbon group having 1 to 15 carbon atoms which may contain O, N or S atoms,
K ⁻ represents a non-nucleophilic counter ion,
x represents 1 or 2,
y represents the integer of 0-3.
[2" claim-type="Currently amended] The resist material according to claim 1, wherein the base resin is a polymer compound having a weight average molecular weight of 1,000 to 500,000 having a repeating unit represented by the following formula (2).
<Formula 2>

Where
R ¹ represents a hydrogen atom, a methyl group or CH ₂ CO ₂ R ³ ,
R ² represents a hydrogen atom, a methyl group or CO ₂ R ³ ,
R ³ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms,
R ⁴ represents a hydrogen atom or a monovalent hydrocarbon group containing a carboxy group or hydroxyl group having 1 to 15 carbon atoms,
At least one of R ⁵ to R ⁸ represents a monovalent hydrocarbon group containing a carboxyl group or a hydroxyl group having 1 to 15 carbon atoms, and the remaining ones each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. , R ⁵ to R ⁸ may form a ring with each other, in which case at least one of R ⁵ to R ⁸ represents a divalent hydrocarbon group containing a carboxy group or hydroxyl group of 1 to 15 carbon atoms, the rest are each independently a single bond Or a linear, branched, cyclic alkylene group having 1 to 15 carbon atoms,
R ⁹ represents a monovalent hydrocarbon group containing a -CO ₂ -partial structure having 3 to 15 carbon atoms,
^At least one of R ¹⁰ to R ¹³ represents a monovalent hydrocarbon group containing a -CO ₂ -substructure having 2 to 5 carbon atoms, and the others are each independently a hydrogen atom or a linear, branched or cyclic group having 1 to 15 carbon atoms. An alkyl group, R ¹⁰ to R ¹³ may form a ring with each other, in which case at least one of R ¹⁰ to R ¹³ represents a divalent hydrocarbon group containing a C 1 -C 15 -CO ₂ -partial structure, and the rest Each independently represents a single bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms,
R ¹⁴ represents an alkyl group containing a polycyclic hydrocarbon group or a polycyclic hydrocarbon group having 7 to 15 carbon atoms,
R ¹⁵ represents an acid labile group,
k represents 0 or 1,
a1, a2, a3, b1, b2, b3, c1, c2, c3, d1, d2, d3, e are zero or more and less than 1, and a1 + a2 + a3 + b1 + b2 + b3 + c1 + c2 + c3 + d1 + d2 + d3 + e = 1 are satisfied.
[3" claim-type="Currently amended] The process of coating the resist material of Claim 1 or 2 on a base material, the process of exposing with light of wavelength 193nm through a photomask after heat processing, and if necessary, using a developing solution after heat processing A pattern forming method comprising the step of developing.

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同族专利:

公开号 | 公开日

US6420085B1|2002-07-16|

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JP2001083695A|2001-03-30|

JP3812622B2|2006-08-23|

引用文献:

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

法律状态:
1999-09-17|Priority to JP99-263257

1999-09-17|Priority to JP26325799A

2000-09-16|Application filed by 카나가와 치히로, 신에쓰 가가꾸 고교 가부시끼가이샤

2001-06-15|Publication of KR20010050483A

优先权:

申请号 | 申请日 | 专利标题

JP99-263257|1999-09-17|

JP26325799A|JP3812622B2|1999-09-17|1999-09-17|Resist material and pattern forming method|

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