Positive photoresist composition

专利摘要:
A resin (a) having a structural unit represented by the following formula and capable of increasing solubility in an alkali-developing solution by decomposition by the action of an acid, and A positive photoresist composition comprising the compound (b) capable of decomposing upon irradiation with actinic radiation or radiation to generate an acid: Here, R1 and R2 may be the same or different, each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R3 and R4 may be the same or different, each may have a hydrogen atom or a substituent , Branched or cyclic alkyl group, R5 represents a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent or an aralkyl group which may have a substituent, and m is The integer of 1-20 is shown and n represents the integer of 0-5.
公开号:KR20000076727A
申请号:KR1020000009219
申请日:2000-02-24
公开日:2000-12-26
发明作者:후지모리토루；탄시로
申请人:무네유키 가코우；후지 샤신 필름 가부시기가이샤；
IPC主号:

专利说明:

Positive Photoresist Composition {POSITIVE PHOTORESIST COMPOSITION}
The present invention relates to a positive photoresist composition used in the manufacture of semiconductor integrated circuit devices, masks for manufacturing integrated circuits, printed wiring boards, liquid crystal panels and the like.
As such positive photoresist compositions, chemically amplified system resist compositions described in US Pat. No. 4,491,628 and European Patent 29,139 are known. The chemically amplified positive resist composition is a pattern-forming reaction in which an acid generated in an exposed portion irradiated with actinic radiation such as far ultraviolet rays or radiation as a catalyst identifies the solubility between the exposed portion and the non-exposed portion in a developer. Material, which provides a pattern to the substrate.
3-component system, consisting of a compound capable of generating an acid by exposing the chemically amplified positive resist composition to an alkali-soluble resin, radiation (photo-acid generator) and a dissolution-inhibiting compound for an alkali-soluble resin, an acid Resin, acid-degradable groups and photo-acids having a two-component system consisting of a resin and a photo-acid generator which can be decomposed by the action of alkali-soluble and a photo-acid generator and a group which is decomposed by the action of an acid and alkali-soluble It can be roughly divided into hybrid systems consisting of low molecular weight dissolution-inhibiting compounds with generators.
JP-A-9-319092 ("JP-A-" as used herein means "non-examined Japanese patent application") contains a resin that is effective in reducing rectified waves with acetal groups injected with oxy bonds. It is open.
In addition, JP-A-10-221854 discloses a resin having a substituted acetal group unit.
However, such resins having rectangular shape of acetal groups and profiles that form a rounded shape at the top are defective and need to improve developing characteristics.
It is an object of the present invention to provide a chemically amplified positive photoresist composition having high sensitivity and high resolution, improving development defects and rectangularity, and having substantially no surface roughness.
Under these circumstances, the inventors of the present invention conducted extensive research and found that the object described above is achieved by a positive photoresist composition composed of a compound containing an acid-degradable group having a specific structure.
More specifically, the object of the present invention is mainly achieved by the following positive photoresist composition.
(1) a resin (a) having a structural unit having a group represented by the following formula (i), which can be decomposed by the action of an acid to increase solubility in an alkaline developer; and
A positive photoresist composition comprising the compound (b) capable of generating an acid by irradiation with actinic radiation or radiation.

Here, R1 and R2 may be the same or different, each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, each of R3 and R4 may be the same or different, each linear or may have a hydrogen atom or a substituent, Represents a branched or cyclic alkyl group, R5 represents a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent or an aralkyl group which may have a substituent, and m is 1 The integer of -20 and n represent the integer of 0-5.
(2) a resin (a) having structural units represented by the following formulas (I), (II) and (III), which can be decomposed by the action of an acid to increase solubility in an alkaline developer; and
Positive photoresist composition comprising compound (b) capable of generating acid by irradiation of radiation or actinic radiation:


Wherein R21 represents a hydrogen atom or a methyl group, R22 represents a group that cannot be decomposed by the action of an acid, R23 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an acyl group or an acyloxy group and n represent the integer of 1-3, W represents the group represented by said formula (i).
(3) In the positive photoresist composition described in the above item (2), the ratio of the structural units (I), (II) and (III) satisfies the following conditions (i) to (iii).
(Iv) 0.10 <(I) / [(I) + (II) + (III)] <0.25,
(Ii) 0.01 <(II) / [(I) + (II) + (III)] <0.15,
(Iii) (I)> (II), and
(Iii) 0.5 <[(I) + (I) + (II)] <0.85
(Here, (I), (II) and (III) represent the molar ratios of the structural units having groups represented by the formulas (I), (II) or (III), respectively.)
(4) In the positive photoresist composition according to any one of items (1) to (3), a compound (b) capable of generating an acid by irradiation with actinic rays or radiation is represented by the following formulas (A-1), (A -2), sulfonic acid can be generated by irradiation of actinic rays or radiation represented by (A-3), (A-4), (A-5), (A-6) and (A-7). At least one compound;

Wherein R ₁ to R ₅ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom or -SR _6- (wherein R ₆ represents an alkyl group or an aryl group) And X ^- is 1) at least one group selected from the group consisting of branched or cyclic alkyl or alkoxy groups having 8 or more carbon atoms, 2) linear, branched or rings having 4 to 7 carbon atoms At least two groups selected from the group consisting of alkyl or alkoxy groups of the type 3) at least three groups selected from the group consisting of linear or branched alkyl or alkoxy groups having from 1 to 3 carbon atoms, 4) 1 to 5 Or anion of benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having a halogen atom or a linear or branched ester group having 1 to 10 carbon atoms;

Here, R ₇ ~ R ₁₀ may be the same or different, each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom, X ^- has the same meaning as defined above, m, n, p , And q each represent an integer of 1 to 3;

Here, R ₁₁ to R ₁₃ may be the same or different, each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom or a -SR ₆ group, X ^- has the same meaning as defined above, 1 , m and n may each be the same or different, and each represents an integer of 1 to 3, and when 1, m and n are 2 or 3, two or three R ₁₁ , R ₁₂ or R ₁₃ groups Any two may combine with each other to form a ring of 5 to 8 elements, including carbon rings, heterocyclic or aromatic rings;

Wherein R ₁₄ to R ₁₆ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom or —SR ₆ , and R ₆ and X ⁻ are the same as defined above Meaning, 1, m and n may be the same or different, respectively, each represents an integer of 1 to 3. When 1, m and n represent 2 or 3, two of two or three groups of each of R ₁₄ , R ₁₅ and R ₁₆ are bonded to each other to form a ring containing 5 to 8 carbon atoms, heterocycles and aromatic rings; It is also possible to form a ring of four elements.

Wherein Y is a linear, branched or cyclic alkyl group which may be substituted, an aralkyl group which may be substituted, or

Wherein R ₃₁ to R ₅₁ may be the same or different and each is hydrogen, linear, branched or cyclic alkyl, alkoxy, acyl, acylamino, sulfonylamino, aryl, acyloxy, If aralkyl or alkoxycarbonyl group, formyl group, nitro group, chlorine atom, bromine atom, iodine atom, hydroxy group or cyano group, and Y may be combined with the residue of another imido sulfonate compound, R ₃₁ to R ₃₅ Two of, two of R ₃₆ to R ₄₂ or two of R ₄₃ to R ₅₁ may combine with each other to form a 5-, 6-, 7- or 8-membered ring of carbon and / or heteroatoms; X is a linear or branched alkylene group which may have substituents, or mono- or polycyclic alkylene groups which may have substituents or contain heteroatoms, provided that X may combine with other imido sulfonate residues. Might be The display is a monocyclic or polycyclic alkenylene group, or an aryl group, an aralkyl Killen which may be substituted, which may be substituted, which may linear or branched alkylene group, a substituted or contain a hetero atom; And

Here, Ar ₁ and Ar ₂ may be the same or different, each represents a substituted or unsubstituted aryl group.
(5) Said positive photoresist composition which further contains cyclic amine compound as described in any one of said (1)-(4) item.
(6) Said positive photoresist composition which further contains at least any one of fluorine-type surfactant and silicone type surfactant as described in any one of said (1)-(5) item.
(7) The positive photoresist composition further comprising a compound which is decomposed by the action of an acid according to any one of items (1) to (6) to increase solubility in an alkaline developer.
The present invention will be described in detail below.
(a) -1: Resin having a structural unit having a group represented by the following formula (Ⅹ), which can be decomposed by the action of an acid to increase solubility in an alkaline developer
In formula (i), the alkyl group represented by R1 or R2 includes 1-4 groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group. There is an alkyl group having a carbon atom.
R3 and R4, which may be the same or different, each represent a hydrogen atom, a linear, branched or cyclic alkyl group which may have substituents.
The linear alkyl group preferably has 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms. Examples thereof include methyl group, ethyl group, n-propyl group, n-butyl group and n-pen. And a n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decanyl group.
The branched alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and examples thereof include i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, i-hexyl group, t-hexyl group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group and t-decanoyl group There is.
The cyclic alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclo group. Heptyl group, cyclooctyl group, cyclononyl group, and cyclodecanoyl group.
R 5 is a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.
The linear or branched alkyl group represented by R 5 preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and examples thereof include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, i-pentyl group, t-pentyl group, n-hexyl group, i-hexyl group, t-hexyl group, n-heptyl group, i-heptyl group, t-heptyl group, n-octyl group, i-octyl group, t-octyl group, n-nonyl group, i-nonyl group, t-nonyl group, n-decanyl group, i-decanyl group, t-decanyl group, i-undecyl group, n-undecyl group, i-undecyl group, n-dodecyl group, i-dodecyl group, n-tridecyl group, i-tridecyl group, n-tetradecyl group, i- Tetradecyl group, n-pentadecyl group, i-pentadecyl group, n-hexadecyl group, i-hexadecyl group, n-heptadecyl group, i-heptadecyl group, n-octadecyl group, i-octade There are practical groups, n-nonadecyl groups and i-nonadecyl groups.
The cyclic alkyl group represented by R 5 preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and the cyclic alkyl group may form a ring having 20 or less carbon atoms, or It may have a substituent. Examples thereof include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecanyl group, cycloundecyl group, cyclododecyl group, cyclotridecyl group, cyclo Tetradecyl group, cyclopentadecyl group, cyclohexadecyl group, cycloheptadecyl group, cyclooctadecyl group, cyclononadecyl group, 4-cyclohexylcyclohexyl group, 4-n-hexylcyclohexyl group, fentanylcyclohexyl group , Hexyloxylcyclohexyl group and fentanyloxycyclohexyl group. In addition, there are cyclic alkyl groups substituted within the range described above.
The aryl group represented by R 5 preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and examples thereof include a phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 3-n-propylphenyl group, 2-n-propylphenyl group, 4-i-propylphenyl group, 3-i-propylphenyl group, 2-i-propylphenyl group, 4-cyclopropylphenyl group, 3-cyclopropylphenyl group, 2-cyclopropylphenyl group, 4-n-butylphenyl group, 3-n-butylphenyl group, 2-n-butylphenyl group, 4-i- Butylphenyl group, 3-i-butylphenyl group, 2-i-butylphenyl group, 4-t-butylphenyl group, 3-t-butylphenyl group, 2-t-butylphenyl group, 4-cyclobutylphenyl group, 3-cyclobutylphenyl group , 2-cyclobutylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 4-cycloheptenylphenyl group, 4-cyclooctanylphenyl group, 2-cyclopentenylphenyl group, 2- Icyclohexylphenyl group, 2-cycloheptenylphenyl group, 2-cyclooctanylphenyl group, 3-cyclopentylphenyl group, 3-cyclohexylphenyl group, 3-cycloheptenylphenyl group, 3-cyclooctanylphenyl group, 4-cyclopentyloxy Phenyl group, 4-cyclohexyloxyphenyl group, 4-cycloheptenyloxyphenyl group, 4-cyclooctanyloxyphenyl group, 2-cyclopentyloxyphenyl group, 2-cyclohexyloxyphenyl group, 2-cycloheptenyloxyphenyl group, 2-cyclo Octanyloxyphenyl group, 3-cyclopentyloxyphenyl group, 3-cyclohexyloxyphenyl group, 3-cycloheptenyloxyphenyl group, 3-cyclooctanyloxyphenyl group, 4-n-pentylphenyl group, 4-n-hexylphenyl group, 4 -n-heptenylphenyl group, 4-n-octanylphenyl group, 2-n-pentylphenyl group, 2-n-hexylphenyl group, 2-n-heptenylphenyl group 2-n-octanylphenyl group, 3-n-pentylphenyl group , 3-n-hexylphenyl group, 3-n-heptenylphenyl group, 3-n-octanylphenyl group, 2,6-di-isopropylphenyl group, 2,3-di- Isopropyl group, a 2,4-di-isopropyl-phenyl, 3,4-di-isopropyl phenyl,
, 3,6-di-t-butylphenyl group, 2,3-di-t-butylphenyl group, 2,4-di-t-butylphenyl group, 3,4-di-t-butylphenyl group, 2,6-di -n-butylphenyl group, 2,3-di-n-butylphenyl group, 2,4-di-n-butylphenyl group, 3,4-di-n-butylphenyl group, 2,6-di-i-butylphenyl group, 2,3-di-i-butylphenyl group, 2,4-di-i-butylphenyl group, 3,4-di-i-butylphenyl group, 2,6-di-t-amylphenyl group, 2,3-di- t-amylphenyl group, 2,4-di-t-amylphenyl group, 3,4-di-t-amylphenyl group, 2,6-di-i-amylphenyl group, 2,3-di-i-amylphenyl group, 2 , 4-di-i-amylphenyl group, 3,4-di-i-amylphenyl group, 2,6-di-n-pentylphenyl group, 2,3-di-n-pentylphenyl group, 2,4-di-n -Pentylphenyl group, 3,4-di-n-pentylphenyl group, 4-ademantylphenyl group, 2-ademantylphenyl group, 4-isoboronylphenyl group, 3-isoboroylphenyl group, 2-isoboroylphenyl group , 4-n-pentyloxyphenyl group, 4-n-hexyloxyphenyl group, 4-n-heptenyloxyphenyl group, 4-n-octanyloxyphenyl group, 2-n-pentyloxyphenyl group, 2-n-hexyloxyphenyl group , 2-n-heptenyloxyphenyl group, 2-n-octanyl Cyphenyl group, 3-n-pentyloxyphenyl group, 3-n-hexyloxyphenyl group, 3-n-heptenyloxyphenyl group, 3-n-octanyloxyphenyl group, 2,6-di-isopropyloxyphenyl group, 2, 3-di-isopropyloxyphenyl group, 2,4-di-isopropyloxyphenyl group, 3,4-di-isopropyloxyphenyl group, 2,6-di-t-butyloxyphenyl group, 2,3-di-t -Butyloxyphenyl group, 2,4-di-t-butyloxyphenyl group, 3,4-di-t-butyloxyphenyl group, 2,6-di-n-butyloxyphenyl group, 2,3-di-n- Butyloxyphenyl group, 2,4-di-n-butyloxyphenyl group, 3,4-di-n-butyloxyphenyl group, 2,6-di-i-butyloxyphenol group, 2,3-di-i-butyl Oxyphenyl group, 2,4-di-i-butyloxyphenyl group, 3,4-di-i-butyloxyphenyl group, 2,6-di-t-amyloxyphenyl group, 2,3-di-t-amyloxy Phenyl group, 2,4-di-t-amyloxyphenyl group, 3,4-di-t-amyloxyphenyl group, 2,6-di-i-amyloxyphenyl group, 2,3-di-i-amyloxyphenyl Group, 2,4-di-i-amyloxyphenyl group, 3,4-di-i-amyloxyphenyl group, 2,3-di-n-pentyloxyphenyl group, 2,6-di-n- Yloxyphenyl group, 2,4-di-n-pentyloxyphenyl group, 3,4-di-n-pentyloxyphenyl group, 4-ademantyloxyphenyl group, 3-ademantyloxyphenyl group, 2-ademantyloxyphenol group, 4-isoboronyloxyphenyl group, 3-isoboroyloxyphenyl group, and 2-isoboroyloxyphenyl group. Each of these groups may be further substituted within the above-described ranges and the substituents are not limited to the above-described ranges.
The aralkyl group represented by R 5 preferably has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and examples thereof include phenylethyl group, 4-methylphenylethyl group, 3-methylphenylethyl group, and 2- Methylphenylethyl group, 4-ethylphenylethyl group, 3-ethylphenylethyl group, 2-ethylphenylethyl group, 4-n-propylphenylethyl group, 3-n-propylphenylethyl group, 2-n-propylphenylethyl group, 4-i-propyl Phenylethyl group, 3-i-propylphenylethyl group, 2-i-propylphenylethyl group, 4-cyclopropylphenylethyl group, 3-cyclopropylphenylethyl group, 2-cyclopropylphenylethyl group, 4-n-butylphenylethyl group, 3- n-butylphenylethyl group, 2-n-butylphenylethyl group, 4-i-butylphenylethyl group, 3-i-butylphenylethyl group, 2-i-butylphenylethyl group, 4-t-butylphenylethyl group, 3-t To -butylphenylethyl group, 2-t-butylphenylethyl group, 4-cyclobutylphenylethyl group, 3-cyclobutylphenylethyl group, 2-cyclobutylphenyl Group, 4-cyclopentylphenylethyl group, 4-cyclohexylphenylethyl group, 4-cycloheptenylphenylethyl group, 4-cyclooctanylphenylethyl group, 2-cyclopentylphenylethyl group, 2-cyclohexylphenylethyl group, 2-cyclohep Tenylphenylethyl group, 2-cyclooctanylphenylethyl group, 3-cyclopentylphenylethyl group, 3-cyclohexylphenylethyl group, 3-cycloheptenylphenylethyl group, 3-cyclooctanylphenylethyl group, 4-cyclopentyloxyphenylethyl group, 4-cyclohexyloxyphenylethyl group, 4-cycloheptenyloxyphenylethyl group, 4-cyclooctanyloxyphenylethyl group, 2-cyclopentyloxyphenylethyl group, 2-cyclohexyloxyphenylethyl group. 2-cycloheptenyloxyphenylethyl group, 2-cyclooctanyloxyphenylethyl group, 3-cyclopentyloxyphenylethyl group, 3-cyclohexyloxyphenylethyl group, 3-cycloheptenyloxyphenylethyl group, 3-cyclooctanyloxyphenyl Ethyl group, 4-n-pentylphenylethyl group, 4-n-hexylphenylethyl group, 4-n-heptenylphenylethyl group, 4-n-octanylphenylethyl group, 2-n-pentylphenylethyl group, 2-n-hexylphenyl Ethyl group, 2-n-heptenylphenylethyl group, 2-n-octanylphenylethyl group, 3-n-pentylphenylethyl group, 3-n-hexylphenylethyl group, 3-n-heptenylphenylethyl group, 3-n-octa Nylphenylethyl group, 2,6-di-isopropylphenylethyl group, 2,3-di-isopropylphenylethyl group, 2,4-di-isopropylphenylethyl group, 3,4-di-isopropylphenylethyl group, 2, 6-di-t-butylphenylethyl group, 2,3-di-t-butylphenylethyl group, 2,4-di-t-butylphenylethyl group, 3,4-di-t-butylphenylethyl group, 2,6- To di-n-butylphenylethyl group, 2,3-di-n-butylphenylethyl group, 2,4-di-n-butylphenyl Group, 3,4-di-n-butylphenylethyl group, 2,6-di-i-butylphenylethyl group, 2,3-di-i-butylphenylethyl group, 2,4-di-i-butylphenylethyl group, 3,4-di-i-butylphenylethyl group, 2,6-di-t-amylphenylethyl group, 2,3-di-t-amylphenylethyl group, 2,4-di-t-amylphenylethyl group, 3, 4-di-t-amylphenylethyl group, 2,6-di-i-amylphenylethyl group, 2,3-di-i-amylphenylethyl group, 2,4-di-i-amylphenylethyl group, 3,4- Di-i-amylphenylethyl group, 2,6-di-n-pentylphenylethyl group, 2,3-di-n-pentylphenylethyl group, 2,4-di-n-pentylphenylethyl group, 3,4-di- n-pentylphenylethyl group, 4-ademantylphenylethyl group, 3-ademantylphenylethyl group, 2-ademantylphenylethyl group, 4-isoboroylphenylethyl group, 3-isoboroylphenylethyl group, 2-isoboro Neylphenylethyl group, 4-n-pentyloxyphenylethyl group, 4-n-hexyloxyphenylethyl group, 4-n-heptenyloxyphenylethyl group, 4-n-octanyloxyphenylethyl group, 2-n-pentyloxyphenylethyl group , 2-n-hexyloxyphenylethyl group, 2-n-heptenyloxyphenylethyl , 2-n-octanyloxyphenylethyl group, 3-n-pentyloxyphenylethyl group, 3-n-hexenyloxyphenylethyl group, 3-n-heptenyloxyphenylethyl group, 3-n-octanyloxyphenylethyl group, 2,6-di-isopropyloxyphenylethyl group, 2,3-di-isopropyloxyphenylethyl group, 2,4-di-isopropyloxyphenylethyl group, 3,4-di-isopropyloxyphenylethyl group, 2, 6-di-t-butyloxyphenylethyl group, 2,3-di-t-butyloxyphenylethyl group, 2,4-di-t-butyloxyphenylethyl group, 3,4-di-t-butyloxyphenylethyl group, 2,6-di-n-butyloxyphenylethyl group, 2,3-di-n-butyloxyphenylethyl group, 2,4-di-n-butyloxyphenylethyl group, 3,4-di-n-butyloxyphenyl Ethyl group, 2,6-di-i-butyloxyphenylethyl group, 2,3-di-i-butyloxyphenylethyl group, 2,4-di-i-butyloxyphenylethyl group, 3,4-di-i-butyl Oxyphenylethyl group, 2,6-di-t-amyloxyphenylethyl group, 2,3-di-t-amyloxyphenylethyl group, 2,4-di-t-amyloxyphenylethyl group, 3,4-di-t -Amyloxyphenylethyl group, 2,6-di-i- Amyloxyphenylethyl group, 2,3-di-i-amyloxyphenylethyl group, 2,4-di-i-amyloxyphenylethyl group, 3,4-di-i-amyloxyphenylethyl group, 2,6-di- n-pentyloxyphenylethyl group, 2,3-di-n-pentyloxyphenylethyl group, 2,4-di-n-pentyloxyphenylethyl group, 3,4-di-n-pentyloxyphenylethyl group, 4-ademantyl Oxyphenylethyl group, 3-ademantyloxyphenylethyl group, 2-ademantyloxyphenylethyl group, 4-isoboroyloxyphenylethyl group, 3-isoboroyloxyphenylethyl group, 2-isoboroyloxyphenylethyl group, And such groups having methyl, propyl or butyl groups instead of alkyl groups. Other examples of such substituents for these groups include hydroxy groups, halogen atoms (eg fluorine, chlorine, bromine, iodine), nitro groups, cyano groups, Alkyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t- described above Alkoxycarbonyl groups such as alkoxy groups, methoxycarbonyl groups and alkoxycarbonyl groups such as benzyl groups, phenethyl groups and cumyl groups, aralkyl groups such as aralkyloxy groups, formyl groups, acetyl groups, butyryl groups, benzo Diary, cinnamic and varyl group, acyloxy group such as butyryloxy group, alkenyl group described above, alkenyloxy group such as vinyloxy group, propenyloxy group, allyloxy group and butenyloxy group, aryl group described above, Aryloxy group such as phenoxy group, and aryloxycarbonyl group such as benzoyloxy group.
As the substituent for R 5, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms is preferable. In addition, these substituents may each have a substituent.
Although the detailed example of the group represented by a formula (i) is set below, this invention is not limited to this.
It has a structural unit having a group represented by the following formula, which is a resin having the group represented by the formula (hereinafter sometimes referred to as a formula), which can be decomposed by the action of acid to increase the solubility in the alkaline developer Is a compound having a structure obtained by injecting an acid-decomposable group represented by the formula (iii) into a compound having a molecular weight dispersion, which becomes alkali-soluble under the action of an acid.
Resin which has group represented by Formula (iii) is resin which has group represented by Formula in both a main chain and a sub chain. Resin which has group represented by a formula on the sub chain is more preferable.
When the group represented by the formula (VII) is bonded to a sub chain, the matrix resin is an alkali-soluble resin having -OH or -COOH on the sub chain, preferably -R ⁰ -COOH or -Ar-OH. For example, an alkali-soluble resin that does not contain an acid-decomposable group described below can be used. In the resin, -R ⁰ -represents a divalent or large aliphatic or aromatic hydrocarbon, and -Ar- represents a divalent or monocyclic or polycyclic large aromatic group, which may have a substituent.
In the present invention, the matrix resin is preferably an alkali-soluble resin having a phenolic hydroxy group.
Alkali-soluble resins having phenolic hydroxy groups used in the present invention are preferably homopolymers or copolymers containing at least 30 mol%, and at least 50 mol% of o-, m- or p-hydroxystyrene (collectively, "Hydroxystyrene") or o-, m- or p-hydroxy- Methylstyrene (collectively these are "hydroxy- Preference is given to resins in which the benzene nucleus of the repeating unit corresponding to -methyl styrene "or the unit described above is partially hydrogenated, but more preferably a p-hydroxystyrene homopolymer.
Copolymerization of the above-mentioned hydroxystyrene or hydroxy- to produce the above-mentioned copolymer. Monomers other than methyl styrene include acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, acrylonitrile, methacrylonitrile, maleic anhydride, styrene, -Methyl styrene, acetoxy styrene, or alkoxy styrene is preferable, and styrene, acetoxy styrene, and t-butoxy styrene are more preferable.
Although content of the repeating unit (structural unit) which has group represented by Formula (X) is 5-50 mol% is preferable on the basis of the sum of all the repeating units, 5-30 mol% is more preferable.
In the present invention, the resin having a group represented by formula (X) may contain other acid-decomposable groups in addition to the group represented by formula (X).
The resin having a group represented by the formula (X) can be obtained by synthesizing the corresponding vinyl ether by a known method and reacting it with a phenol hydroxy group-containing alkali soluble resin dissolved in a suitable solvent such as tetrahydrofuran. The reaction is generally carried out in the presence of an acidic catalyst. Preference is given to salts such as acidic ion exchange resins, hydrochloric acid, p-toluenesulfonic acid or pyridinium tosylate. The corresponding vinyl ethers may be synthesized from nucleophilic substitution reactions or the like from an active starting material such as chloroethyl vinyl ether or by using a mercury or palladium catalyst.
The corresponding vinyl ethers may also be synthesized using the corresponding alcohols and vinyl ethers by the acetal exchange method. In this case, the alcohol has a substituent that is artificially injected, and the vinyl ether may have a relative labile ether to be mixed therewith, in which the reaction is carried out of an acid such as p-toluenesulfonic acid or pyridinium tosylate. Will be done in presence.
Although it is good to have a weight average molecular weight of 3,000-80,000 with the said resin which has group represented by Formula (X), it is more preferable to have 5,000-50,000. The molecular weight distribution (Mw / Mn) is generally 1.01 to 4.0, but 1.05 to 3.00 is preferable. In order to obtain a polymer having such a molecular weight distribution, it is preferable to use anionic polymerization or radical polymerization.
Although the detailed structure of the said resin which has group represented by Formula (X) is shown below, this invention is not limited to this illustration at all.

For example, in the resin used in the present invention, such as a resin having a group represented by formula (X) and a resin having a structural unit represented by formulas (I), (II) and (III), The cross-linking portion connecting the acetal groups of the multifunctional group may be injected by adding a polyhydroxy compound at the stage of the synthesis to control the dissolution rate in alkali or improve the thermal resistance.
Although the quantity of the said polyhydroxy compound added is 0.01-10 mol% based on the number of hydroxy groups in resin, 0.05-8 mol% is preferable and 0.1-5 mol% is more preferable.
Although the said polyhydroxy compound has 2-6 phenolic hydroxyl group or alcohol hydroxy group, it is preferable to have 2-4 hydroxyl groups, and it is more preferable to have 2-3 hydroxyl groups. Detailed examples thereof are shown below, but the present invention is in no way limited to these examples.
(a) -2: Resin which has structural units represented by following formula (I), (II), and (III) which can decompose | dissolve by the action of an acid and can increase solubility in alkaline developing solution.
R21 represents a hydrogen atom or a methyl group.
Examples of groups that cannot be decomposed by the action of an acid represented by R 22 (also referred to as “acid-stable groups”) include a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, and an alkyloxy group ( -O- tertiary alkyl), acyl group, cycloalkyloxy group, alkenyloxy group, aryloxy group, alkylcarbonyloxy group, alkylamide methyloxy group, alkylamide group, arylamide methyl group and arylamide group have. Although the acyl group, the alkylcarbonyloxy group, the alkyloxy group, the cycloalkyloxy group, the aryloxy group, the alkylamideoxy group or the akylamide group is preferable, the acid stability group may be an acyl group, an alkylcarbonyloxy group or an alkyl jade. The timing, cycloalkyloxy group or aryloxy group is more preferable.
In the acid stability group represented by R22, the alkyl group is an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec butyl group and t-butyl group; The cycloalkyl group may be a cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and an admantyl group; The alkenyl group is an alkenyl group having 2 to 4 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group; The aryl group is an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a silyl group, toluyl group, cumenyl group, naphthyl group, and atracenyl group; The alkoxy group has an alkoxy group having 1 to 4 carbon atoms such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group and sec-butoxy group, respectively. desirable.
The halogen atom represented by R 23 is fluorine, chlorine, bromine or iodine; The alkyl group is an alkyl group having 1 to 8 carbon atoms such as methyl, ethyl, propyl, n-butyl, sec-butyl, t-butyl, hexyl and octyl; The aryl group is an aryl group having 6 to 14 carbon atoms such as phenyl, krill, toluyl, comenyl, naphthyl and anthracenyl; The alkoxy group has an alkoxy group having 1 to 4 carbon atoms such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, n-butoxy, isobutoxy, sec-butoxy and t-butoxy ; The acyl group may be an acyl group having 1 to 7 carbon atoms such as formyl, acetyl, propanoyl, butanoyl and benzoyl; And the acyloxy group is preferably an acyloxy group having 2 to 7 carbon atoms such as acetoxy, propanoyloxy, butanoyloxy and benzoyloxy.
Substituent W in Formula (I) is the same as defined in Formula (iii) described above.
Examples of the structural unit represented by formula (I) are illustrated below.

Since the resin contains the structural unit represented by formula (II), the resin can be decomposed by the action of an acid, and the solubility in the alkaline developer can be controlled. In addition, by injecting such structural units, a profile having excellent rectangularity can be obtained. In addition, this structural unit is effective in controlling the amount of the structural unit represented by the formula (I).
Detailed examples of the polymerizable monomer having a structural unit represented by formula (II) will be illustrated below, but the present invention is by no means limited to these examples.
The resin containing the structural unit represented by formula (I), (II) or (III) can be obtained by reacting a monomer or phenol resin related thereto with an acid anhydride or a corresponding halide in the presence of a base.
In the present invention, the resin which can be decomposed by the action of an acid to increase the solubility in the alkali-developing solution is added to the structural units represented by the formulas (I), (II) and (III) to form other copolymerized components. It may contain a monomer unit.
In the present invention, the proportion of the structural units represented by the formulas (I), (II) and (III) preferably satisfies the following conditions (i) to (i):
(Iv) 0.10 <(I) / [(I) + (II) + (III)] <0.25,
(Ii) 0.01 <(II) / [(I) + (II) + (III)] <0.15,
(Iii) (I)> (II), and
(Iii) 0.5 <(I) / [(I) + (II)] <0.85
(Here, (I), (II) and (III) represent the molar ratios of the structural units having groups represented by the formulas (I), (II) and (III), respectively.)
When the resin of the present invention satisfies the conditions described above, the profile is improved in rectangularity, and in particular, the development defect is further improved.
The repeating structural units each derived from other polymerizable monomers and the repeating structural units represented by formulas (I), (II) and (III) may be present alone or in combination of two or more thereof.
In the resin contained in the positive photosensitive composition of the present invention, suitable other polymerizable monomers are copolymerized in order to inject an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group to maintain good developability with an alkaline developer. It may be.
Resin having a repeating structural unit represented by the formula (I), (II) and (III) synthesized by the above-described method has an average weight (Mw, polystyrene basis) of 2,000 or more as the molecular weight, when 3,000 to 200,000 Although it is preferable, it is more preferable in it being 5,000-70,000. Dispersion degree (Mw / Mn) is preferably 1.0 to 4.0, more preferably 1.0 to 3.5, and even more preferably 1.0 to 3.0. The smaller the degree of dispersion, the better the thermal resistance and image forming characteristics (e.g., pattern profile, defocus latitude).
50-99 weight% of content of resin which has a structural unit represented by Formula (I), (II) and (III) in this positive photosensitive composition (except coating solvent) is 70-97 weight% further good.
Although the detailed example of the said resin which has a repeating structural unit represented by Formula (I), (II), and (III) will be illustrated below, this invention is not limited only to this illustration at all.



In the present invention, in addition to the resin having a repeating structural unit represented by formulas (I), (II) and (III), a resin having other acid-decomposable groups may be used in the form of a binder. Other resins that can be degraded by acid to increase solubility in alkaline developer can be used in the chemically amplified resists of the present invention, which have groups that can be degraded by acid in their backbone or in the backbone or both backbones and backbones. It is a resin. Resin which has a group which can be decomposed by an acid in a side chain is preferable.
Preferred groups that can be decomposed by acid are -COOA ⁰ or -OB ⁰ . Examples of groups containing such groups include groups represented by -R ⁰ -COOA ⁰ and -Ar-OB ⁰ .
A ⁰ represents -C (R ¹ ) (R ² ) (R ³ ), -Si (R ¹ ) (R ² ) (R ³ ) or -C (R ⁴ ) (R ⁵ ) -OR ⁶ , B ⁰ is -A ⁰ or -CO-OA ⁰ (wherein R ⁰ , R ¹ to R ⁶ and Ar have the same meaning as will be described below.)
As the acid-decomposable group, a silyl ether group, cumyl ester group, acetal group, tetrahytropyranyl ester group, enol ether group, enol ester group, quaternary alkyl ether group, quaternary alkyl ester group or quaternary alkyl Carbonate groups are preferred, of which quaternary alkyl ester groups, quaternary alkyl carbonate groups, cumyl ester groups, acetal groups or tetrahydropyranyl ether groups are more preferred.
When the above-described group which can be decomposed by an acid is bonded to the sub chain, the matrix resin is alkali-soluble having -OH or -COOH in the sub chain, preferably -R ⁰ -COOH or -Ar-OH. Resin. Examples thereof include alkali-soluble resins described below.
Alkali-soluble resins preferably have a (23 ° C.) alkali dissolution rate determined by 0.261 N tetramethylammonium hydroxide (TMAH) of at least 170 A / sec, more preferably of at least 33 0 A / sec (A is Angstrom).
In addition, in terms of making a rectangular profile, the alkali-soluble resin has excellent transmission power to far ultraviolet rays or excimer laser lines. As for the said transmission rate of the line whose thickness is 1 micrometer and the wavelength is 248 nm, 20 to 90% is preferable.
In this aspect, preferred examples of the alkali-soluble resins include o-, m- and p-poly (hydroxystyrene) and copolymers thereof, hydrotreated poly (hydroxystyrene), halogen or alkali-substituted poly (Hydroxystyrene), partially O-alkylated or O-acylated poly (hydroxystyrene), styrene-hydroxystyrene copolymers, -Methylstyrene-hydroxystyrene copolymers and hydrotreated novolak resins.
The resin having a group which can be decomposed by an acid used in the present invention reacts a precursor of an acid-decomposable group with an alkali-soluble resin, or an alkali-soluble resin monomer having an acid-decomposable group combined with various kinds of monomers. It can obtain by copolymerizing.
In combination with the resin having an acid-decomposable group and a photo-acid generator, an acid-degradable low molecular dissolution-inhibiting compound described below may be mixed.
The acid-degradable low molecular dissolution-inhibiting compound used in the present invention has at least two groups that can be decomposed by an acid, and the distance between the acid-decomposable groups at the furthest position excludes at least 8 Compound having a structure that allows two atoms to pass through.
The acid-degradable low molecular weight dissolution-inhibiting compound used in the present invention may contain at least one acid-decomposable group represented by formula (X).
In the present invention, the acid-degradable dissolution-inhibiting compound has at least two groups capable of decomposing into an acid, and the distance between the acid-degradable groups at the furthest position is at least 10 excluded binding atoms of the acid-decomposable group, Preferably there are 11, more preferably 12, or at least three acid-decomposable groups, and the distance between the acid-decomposable groups at the furthest position is such that the excluded binding atoms of the acid-decomposable groups are at least It is preferred that the structure pass through nine, preferably ten, most preferably eleven. The upper limit of the number of bonding atoms is 50, but 30 is better.
In the present invention, when the acid-decomposable dissolution-inhibiting compound contains three or more preferably four or more acid-decomposable groups or even when the compound contains two acid-decomposable groups, the alkali-soluble resin The dissolution-inhibition property is significantly increased by the acid-decomposable groups separated from each other at a predetermined distance.
In the present invention, the distance between the acid-decomposable groups is expressed by the number of binding atoms present between the excluded acid-decomposable groups. For example, in each of the following compounds (1) and (2), the distance between the acid-decomposable groups is four bond atoms, and the distance between the acid-decomposable groups in compound (3) is represented by 12 binding atoms.
Acid-degradable group: -COO-A ⁰ or -OB ⁰
Although the dissolution-inhibiting compound used in the present invention may have a plurality of acid-decomposable groups in one benzene ring, a compound composed of a skeleton having one acid-decomposable group by one benzene ring is preferable. Although the compound comprised from the skeleton which has one acid-decomposable group in one benzene ring used for this invention has a molecular weight of 3,000 or less, it is preferable that it is 500-3,000, and it is more preferable that it is 1,000-2,500.
In a preferred embodiment of the invention, examples of groups which can be decomposed into acids, for example, groups containing -COO-A ⁰ or -OB ⁰ are represented by -R-COO-A ⁰ or -Ar-OB ⁰ There is a flag.
A ⁰ represents -C (R ¹ ) (R ² ) (R ³ ), -Si (R ¹ ) (R ² ) (R ³ ) or -C (R ⁴ ) (R ⁵ ) -OR ⁶ , B ⁰ represents -A ⁰ or -CO-OA ⁰ .
R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and if at least two of R ¹ to R ³ are R ⁶ represents an alkyl group or an aryl group as long as it is a group except a hydrogen atom and at least two groups of R ⁰¹ and R ³ or R ⁴ to R ⁶ may be bonded to form a ring. R ⁰ represents a divalent or expensive aliphatic or aromatic hydrocarbon group which may have a substituent, and -Ar- represents a divalent or expensive aromatic group which is monocyclic or polycyclic, which may have a substituent.
The alkyl group is an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and t-butyl group; The cycloalkyl group may be a cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and an admantyl group; The alkenyl group is an alkenyl group having 2 to 4 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group; The aryl group is preferably each an aryl group having 6 to 14 carbon atoms such as phenyl group, xyl group, toluyl group, cumenyl group, naphthyl group and anthracenyl group.
Examples of the substituent include hydroxy group, halogen atom (e.g., fluorine, chlorine, bromine, iodine), nitro group, cyano group, alkyl group described above, methoxy group, ethoxy group, propoxy group, hydroxyethoxy group, hydroxy Alkoxycarbonyl groups such as oxypropoxy groups, n-butoxy groups, isobutoxy groups, sec-butoxy groups and t-butoxy groups, such as alkoxycarbonyl groups such as methoxycarbonyl groups and ethoxycarbonyl groups, benzyl groups, phenethyl groups and cumyl groups Aralkyl groups, aralkyloxy, formyl groups, acetyl groups, butyryl groups, benzoyl groups, acyl groups such as cinnamil groups and varyl groups, acyloxy groups such as butyryloxy groups, alkenyl groups, vinyloxy groups and propenyls described above Alkenyloxy groups such as oxy group, allyloxy group and butenyloxy group, aryl groups described above, aryloxy groups such as phenoxy group and aryloxycarbonyl groups such as benzoyloxy group.
Examples of the group decomposed by the acid include a silyl ether group, cumyl ester group, acetal group, tetrahydropyranyl ether group, enol ether group, enol ester group, quaternary alkyl ether group, quaternary alkyl ester group or agent. Quaternary alkyl carbonate groups are preferred, of which quaternary alkyl ester groups, quaternary alkyl carbonate groups, cumyl ester groups or tetrahydropyranyl ether groups are more preferred.
Preferred examples of the acid-degradable dissolution-inhibiting compound include groups described above, such as -R ⁰ -COO-A ⁰ -or B ⁰ , JP-A-1-289946, JP-A-1-289947, JP- A-2-2560, JP-A- 3-128959, JP-A-3-158855, JP-A-3-179353, JP-A-3-191351, JP-A-3-200251, JP-A- 3- 200252, JP-A-3-200253, JP-A-3-200254, JP-A-3-200255, JP-A-3-259149, JP-A-3 -279958, JP-A-3- 279959, JP-A-4-1650, JP-A-4-1651, JP-A-4-11260, JP-A-4-12356, and JP-A-4-12357, Japanese Patent Application Nos. Phenol OH groups of the polyhydroxy compounds described in 3-33229, 3-230790, 3-320438, 4-25157, 4-52 732, 4-103215, 4-104542, 4-207885, 4-107889 and 4-152195 There are compounds that are protected by binding to some or all of the compounds.
Among these, more preferable examples are JP-A-1-289946, JP-A-3-128959, JP-A-3-1588 55, JP-A-3-179353, JP-A-3-200251, JP-A -3-200252, JP-A-3-200255, JP-A-3-2591 49, JP-A-3-279958, JP-A-4-1650, JP-A-4-11260, JP-A- 4-12356, JP-A-4-12357, and Japanese Patent Application Nos. The polyhydroxy compounds described in 4-25157, 4-103215, 4-104542, 4-107885, 4-107889 and 4-15 2195 are used.
Specific examples thereof include compounds represented by the formulas [I] to [XVI].
Wherein R ¹⁰¹ , R ¹⁰² , R ¹⁰⁸ and, R ¹³⁰ may be the same or different and each is a hydrogen atom, -R ⁰ -COO-C (R ¹ ) (R ² ) (R ³ ) or -CO-OC Denotes (R ¹ ) (R ² ) (R ³ ), where R ⁰ , R ¹ , R ² and R ³ have the same meanings as defined above.
R ¹⁰⁰ is -CO-, -COO-, -NHCONH-, -NHCOO-, -O-, -S-, -SO-, -SO _2- , -SO ₃ -or
Is displayed.
(If G is 2, if at least one of R ¹⁵⁰ and R ¹⁵¹ is an alkyl group, G is a number from 2 to 6.)
R ¹⁵⁰ and R ¹⁵¹ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, -OH, -COOH, -CN, a halogen atom, -R ¹⁵² -COOR ¹⁵³ or -R ¹⁵⁴ -OH, R ¹⁵² and R ¹⁵⁴ each represent an alkylene group.
R ¹⁵³ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.
R ⁹⁹ , R ¹⁰³ to R ¹⁰⁷ , R ¹⁰⁹ , R ¹¹¹ to R ^118, and R ¹³¹ to R ¹³⁴ may be the same or different, and each may represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, or an aryl. Group, aryloxy group, aralkyl group, aralkyloxy group, halogen atom, nitro group, carboxy group, cyano group or -N (R ¹⁵⁵ ) (R ¹⁵⁶ ) is represented, wherein R ¹⁵⁵ and R ¹⁵⁶ are each represented by H, An alkyl group or an aryl group is represented.)
R ¹¹⁰ is a single bond, an alkylene group or
Is displayed.
Wherein R ¹⁵⁷ and R ¹⁵⁹ may be the same or different and each represents a single bond, an alkylene group, -O-, -S-, -CO-, or a carboxy group,
R ¹⁵⁸ is ^substituted with the hydroxy group by an acid-decomposable group (eg, T-butoxycarbonylmethyl group, tetrahydropyranyl group, 1-ethoxy-1-ethyl group, 1-t-butoxy-1-ethyl group) If possible, a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, a nitro group, a hydroxy group, a cyano group or a carboxy group is represented,
R ¹¹⁹ and R ¹²⁰ may be the same or different, and if the low alkyl group used in the present invention means an alkyl group having 1 to 4 carbon atoms, each of methylene group, low alkyl-substituted methylene group, halomethylene group Or a haloalkylene group,
A represents a methylene group, a low alkyl-substituted methylene group, a halomethylene group or a haloalkylene group,
When a to v and g1 to i1 are each plural, many of the groups in parentheses may be the same or different.
a to q, s, t, v, g1 to i1 and k1 to m1 each represent an integer of 0 or 1 to 5,
r and u represent 0 or an integer of 1 to 4, respectively,
j1 and n1 represent 0 or an integer of 1 to 3, respectively
(a + b), (d + f + g), (k + l + m), (q + r + s), (g1 + h1 + i1 + j1) 2,
(j1 + n1) 3,
(r + u) 4,
(a + c), (b + d), (e + h), (f + i), (g + j), (k + n), (l + o), (m + p), (q + t), (s + v), (g1 + k1), (h1 + l1) and (i1 + m1) 5;
Wherein R ¹⁶⁰ represents an organic group, a single bond, -S-, -SO- or Display the
R ¹⁶¹ is a hydrogen atom, a monovalent organic group or (Where R ¹⁶² to R ¹⁶⁶ may be the same or different and at least two are -OR ⁰ -COO-C (R ¹ ) (R ² ) (R ³ ) or -O-CO-OC (R ¹ ) (R ² ) (R ³ ), and when 4 to 6 substituents having the same symbol are the same or different, each is a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, -OR ⁰ -COO-C (R ¹ ) (R ² ) (R ³ ) or -O-CO-OC (R ¹ ) (R ² ) (R ⁰³ )
X represents a divalent organic group,
e2 represents 0 or 1;
Here, R ¹⁶⁷ to R ¹⁷⁰ may be the same or different, and in the case where 4 to 6 substituents having the same symbol may be the same or different, each of a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group, an alkoxy group or an alkenyl group Display.
R ¹⁷¹ and R ¹⁷² each represent a hydrogen atom, an alkyl group or Is displayed.
At least two of the R ¹⁷³ groups are -OR ⁰ -COO-C (R ¹ ) (R ² ) (R ³ ) or -O-CO-OC (R ¹ ) (R ² ) (R ⁰³ ), with the remainder It is a hydroxyl group,
f2 and h2 represent 0 or 1, respectively,
g2 represents 0 or an integer of 1 to 4; And,
Here, R ¹⁷⁴ ~ R ¹⁸⁰ may be the same or different, and if six substituents having the same symbol may be the same or different, each of the hydrogen atom, hydroxy group, halogen atom, alkyl group, alkoxy group, nitro group, alkenyl group , Aryl group, aralkyl group, alkoxycarbonyl group, arylcarbonyl group, acyloxy group, acyl group, aralkyloxy group or aryloxy group,
At least two of the R ¹⁸¹ groups are -OR ⁰ -COO-C (R ¹ ) (R ² ) (R ³ ) or -O-CO-OC (R ¹ ) (R ² ) (R ⁰³ ), the remainder being It is a hydroxyl group.
Detailed examples of preferred compound skeletons are illustrated below.



In compounds (1) to (43), if at least two, at least three groups except hydrogen atom and substituent R in each compound may be the same or different depending on the structure, R is a hydrogen atom, -CH ₂ -COO- C (CH ₃ ) ₂ C ₆ H ₅ , -CH ₂ -COO-C ₄ H ₉ (t), -COO-C ₄ H ₉ (t) or Is displayed.
In this case, the content of the dissolution-inhibiting compound is generally from 3 to 45% by weight, preferably from 5 to 30% by weight, based on the total weight of the photosensitive composition (excluding the solvent). More preferred.
In order to control alkali solubility, it is also possible to mix alkali-soluble resins having no groups that can be decomposed by acid.
Examples of such alkali-soluble resins include novolak resins, hydrogenated novolak resins, acetone-pyrogallol resins, o-polyhydroxystyrenes, m-polyhydroxystyrenes, p-polyhydroxystyrenes, hydrogenated polys Hydroxystyrene, halogen- or alkali-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- or m / p-hydroxystyrene copolymer, a portion of the hydroxy group being O- Alkylated polyhydroxystyrene (eg, 5-30 mol% O-methylated) or O-acylated polyhydroxystyrene (eg, 5-30 mol% O-acetylated), styrene-maleic acid Anhydride copolymers, styrene-hydroxystyrene copolymers, -Methylstyrene-hydroxystyrene copolymers, carboxyl group-containing methacryl-base resins and derivatives thereof, although the present invention is by no means limited to these examples.
Among these alkali-soluble resins, novolak resins; o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, partially O-alkylated or O-acylated polyhydroxy Styrene, styrene-hydroxystyrene copolymers, and Preference is given to -methylstyrene-hydroxystyrene copolymers. The novolak resin can be obtained by addition-condensation of a predetermined main component monomer with anhydride, under an acidic catalyst.
Examples of such predetermined monomers include cresols such as phenol, m-cresol, p-cresol and o-cresol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol and 2, Xylenol, such as 3-xylenol, alkylphenols such as m-ethylphenol, p-ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol and 2,3,5-trimethylphenol, p -Methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-prop Alkoxyphenols such as foxyphenol, m-butoxyphenol and p-butoxyphenol, bisalkylphenols such as 2-methyl-4-isopropylphenol and m-chlorophenol, p-chlorophenol, o-chlorophenol, di Hydroxy aromatic compounds such as hydroxybiphenyl, bisphenol A, phenylphenol, risolecinol and naphthiol and these monomers may be used alone or in the form of two or more combinations. However, the present invention is by no means limited thereto.
Examples of such aldehydes that may be used include formaldehyde, p-formaldehyde, acetoaldehyde, propionaldehyde, benzaldehyde, phenylacetoaldehyde, Pennylypropyl aldehyde, -Phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-hydroxybenzaldehyde Acetal forms such as nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, pure, chloroacetaldehyde and chloroacetaldehyde diethyl acetal Of these, formaldehyde is preferred.
Such formaldehyde may be used either alone or in the form of a combination of two or more. Examples of such acidic catalysts that may be used are hydrochloric acid, sulfuric acid, formic acid, acetic acid and oxalic acid.
It is preferable that the said novolak resin has a weight average molecular weight of 1,000-30,000. When the weight average molecular weight is less than 1,000, the layer loss of the non-exposed part after development becomes large, whereas if it exceeds 30,000, the development ratio decreases. The weight average molecular weight is more preferably 2,000 to 20,000.
In addition to the novolak resin, each of the polyhydroxystyrene and its derivatives and copolymers has a weight average molecular weight of 2,000 or more, preferably from 5,000 to 200,000, more preferably from 10,000 to 100,000. In view of improving the thermal resistance of the resist film, the weight average molecular weight may be 25,000 or more.
The weight average molecular weight used herein is defined as polystyrene-reduced value by gel permeation chromatography.
In the present invention, the alkali-soluble resin described above may be used in the form of a combination of two or more thereof.
As for the addition amount of alkali-soluble resin added to the said composition, 5-30 weight% is preferable.
The photo-acid generator (b) used in the present invention is a compound capable of generating an acid by irradiation with actinic rays or radiation.
Compounds which can be decomposed by irradiation of actinic rays or radiation used in the present invention to generate an acid are photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photobleaching agents such as dyes, photobleaching agents, microresists and the like. Light (e.g., ultraviolet or far ultraviolet rays of 200-400 nm, in particular g-rays, h-rays, i-rays, KrF excimer laser rays), ArF excimer laser rays, electron beams, X-rays, molecular beams or There are compounds that can generate acids by irradiation of ion beams, and mixtures thereof.
Compounds that can generate acids by irradiation of actinic radiation or radiation used in the present invention include onium salts, organic halogen compounds such as diazonium salts, ammonium salts, phosphonium salts, iodonium, sulfonium salts, selenium salts and arzonium salts , Organic metal / organic halogen compounds, photo-acid generators with o-nitrobenzyl type protecting groups, compounds capable of photolysis to generate sulfonic acids, compounds represented by iminosulfonates, and disulfone compounds.
In addition, a compound in which an acid or a compound capable of generating an acid by irradiation with light described above is injected into the main chain or the sub chain of the polymer may be used.
See also V.N.R Pillai, Synthesis, (1), 1 (1980), A. Absd et al., Tetrahe dron Lett., (47), 4555 (1971), D.H.R. Barton et al., J. Chem. Soc., (C), 329 (19 70), US Pat. No. 3,779,778 and European Patent 126,712 may also be used compounds which can generate an acid by irradiation of light.
Of these compounds which can be decomposed by irradiation of actinic radiation or radiation, compounds which can generate sulfonic acid by irradiation of actinic radiation or radiation represented by formulas (A-1) to (A-7) are preferred. .
The compounds represented by formulas (A-1) to (A-7) will be described in detail below.
Photo-acid generator represented by formula (A-1)-(A-3)
Examples of the alkyl group represented by any one of R ₁ to R ₆ and R ₇ to R ₁₀ of formulas (A-1) to (A-3) include a methyl group, an ethyl group, a propyl group, n having 1 to 4 carbon atoms There are alkyl groups such as -butyl group, sec-butyl group and t-butyl group, which may have a substituent. Examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group having 3 to 8 carbon atoms, which may have a substituent. Examples of the alkoxy group include alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy group, n-butoxy, isobutoxy, sec-butoxy and t-butoxy having 1 to 4 carbon atoms. . Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom. Examples of the aryl group include an aryl group such as a phenyl group, tolyl group, methoxyphenyl group and naphthyl group having 6 to 14 carbon atoms, which may have a substituent.
Preferred examples of the substituent include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (for example, fluorine, chlorine, iodine), an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, Cyano, hydroxy, carboxyl, alkoxycarbonyl and nitro groups.
The sulfonium or iodonium compound represented by formulas (A-1), (A-2) and (A-3) used in the present invention is a covalent ion X ⁻ , at least 8, preferably at least 10 carbon sources Containing at least one branched or cyclic alkyl or alkoxy group having at least two, at least two linear, branched or cyclic alkyl or alkoxy groups having from 4 to 7 carbon atoms, and having at least 1 to 3 carbon atoms Benzene sulfonic acid, naphthalenesulfonic acid or anthracene sulfonic acid containing three linear or branched alkyl or alkoxy groups and containing linear, branched or cyclic ester groups having 1 to 5 halogen atoms or 1 to 10 carbon atoms It contains anion of phonic acid. As a result, the diffusion rate of the acid (benzenebenzene, phthalene sulfonic acid or anthracene sulfonic acid having a group to be described below) occurring after exposure is reduced and the solvent solubility of the sulfonium or iodonium compound is increased. Specifically, in view of reducing the diffusion rate, the group is preferably a branched or cyclic alkyl group or an alkoxy group, rather than a linear alkyl group or an alkoxy group. In the case where the number of groups is 1, the diffusion rates between linear and branched groups and cyclic groups are more surely different.
Examples of the alkyl group having 8 or more, preferably 8 to 20 carbon atoms include octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group and octadecyl group, which are side chains It may be in the form of a ring or a ring.
Examples of the alkoxy group having 8 or more, preferably 8 to 20 carbon atoms include octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group and There are octadecyloxy groups, which may be branched or cyclic.
Examples of the alkyl group having 4 to 7 carbon atoms include butyl group, pentyl group, hexyl group and heptyl group, which may be linear, branched or cyclic.
Examples of the alkoxy group having 4 to 7 carbon atoms include butoxy group, pentyloxy group, hexyloxy group and heptyloxy group, which may be linear, branched or cyclic.
Examples of the alkyl group having 1 to 3 carbon atoms include methyl group, ethyl group, n-propyl group and isopropyl group.
Examples of the alkoxy group having 1 to 3 carbon atoms include methoxy, ethoxy, n-propoxy group and isopropoxy group.
Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom, with fluorine atom being preferred.
Examples of linear, branched or cyclic esters having 1 to 10 carbon atoms include methyl ester groups, ethyl ester groups, n-propyl ester groups, i-propyl ester groups, n-butyl ester groups, i-butyl ester groups, t-butyl ester group, n-hexyl ester group, i-hexyl ester group, t-hexyl ester group, n-heptyl ester group, i-heptyl ester group, t-heptyl ester group, n-octyl ester group, i- Octyl ester group, t-octyl ester group, n-nonyl ester group, i-nonyl ester group. t-nonyl ester group, n-decanyl ester group, i-decanyl ester group, t-decanyl ester group, cyclopropyl ester group, cyclobutyl ester group. There are a cyclopentyl ester group, a cyclohexyl ester group, a cycloheptyl ester group, a cyclooctyl ester group, a cyclononyl ester group, and a cyclodecanyl ester group,
In addition to the specific substituents described above, the aromatic sulfonic acid represented by X ⁻ is a halogen atom (for example, fluorine, chlorine, bromine, iodine), an aryl group having 6 to 10 carbon atoms, a cyano group, It may contain a sulfide group, a hydroxyl group, a carboxyl group or a nitro group.
Detailed examples of such compounds (A-1-1) to (A-1-66), (A-2-1) to (A-2-59), and (A-3-1) to (A-3- Although 35) is shown below, the present invention is in no way limited to this example.







In this detailed example, "n", "s", "t" and "i" indicate "primary", "secondary", "tertiary" or "side chain" respectively.
A compound represented by formulas (A-1) to (A-3) and a compound represented by X ^- Y ⁺ (wherein X ^- has the same meaning as in formulas (A-1) to (A-3), Y ⁺ denotes cations such as H ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ and N (CH ₃ ) ₄ ⁺ . For example, salt-exchange of the corresponding Cl ⁻ salt in aqueous solution. in a-1) ~ (a- 3) Cl - can also be synthesized by the method according to one alternative the compound) ^- X a.
Photo-acid generator represented by formulas (A-4) and (A-5)
In formulas (A-4) and (A-5), a detailed example of the alkyl group, the cycloalkyl group, the alkoxy group and the halogen atom represented by any one of R ₁₁ to R ₁₃ and R ₁₄ to R ₁₆ is R _1. It is the same as what was described above about R <_5> . R ₆ and X ⁻ have the same meaning as defined above.
When 1, m and n are each 2 or 3, two of two or three R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ or R ₁₆ groups are bonded to each other to form a carbon ring, heterocyclic ring or aromatic ring It can also form a ring consisting of five or eight components, including.
Detailed examples represented by formula (A-4) (A-4-1) to (A-4-28) and detailed examples represented by (A-5) (A-5-1) to (A-5-) 30) is shown below, but the invention is in no way limited to this example.



In this detailed example, "n", "s", "t" and "i" indicate "primary", "secondary", "tertiary" or "side chain" respectively.
A compound represented by formulas (A-4) and (A-5) and a compound represented by X ^- Y ⁺ , wherein X ^- has the same meaning as in formulas (A-4) and (A-5), Y ⁺ denotes cations such as H ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ and N (CH ₃ ) ₄ ⁺ . For example, salt-exchange of the corresponding Cl ⁻ salt in aqueous solution. in a-4) and (a-5) Cl ^- can also be synthesized by the method according to one alternative the compound) ^- X a.
Photo-acid generator represented by formula (A-6)
In the formula (A-6), the linear, branched or cyclic alkyl group represented by any one of Y and R ₃₁ to R ₅₁ may be methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, There are linear or branched alkyl groups having 1 to 20 carbon atoms such as t-butyl group, hexyl group and octyl group, cyclic alkyl groups such as cyclopropyl group, cyclopentyl group and cyclohexyl group. As a substituent of the said alkyl group, an alkoxy group, an acyl group, an acyloxy group, a chlorine atom, a bromine atom, and an iodine atom are preferable.
Examples of the aralkyl group represented by Y include aralkyl groups having 7 to 12 carbon atoms such as benzyl and phenethyl groups. Substituents for the aralkyl group include a low alkyl group having 1 to 4 carbon atoms, a low alkoxy group having 1 to 4 carbon atoms, a nitro group, an acetylamino group or a halogen atom.
Examples of the alkoxy group represented by any one of R ₃₁ to R ₅₁ include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, There are alkoxy groups having substituents such as ethoxyethoxy groups and alkoxy groups having 1 to 20 carbon atoms such as octyloxy group and dodecyloxy group. Examples of the acyl group include an acetyl group, propionyl group and benzoyl group. Examples of the acylamino group include an acetylamino group, propionylamino group and benzoylamino group. Examples of the sulfonyl amido groups include sulfonylamino groups having 1 to 4 carbon atoms such as methanesulfonylamino group and ethanesulfonylamino group and substituted or unsubstituted benzenesulfonylamino group such as p-toluenesulfonylamino group. Examples of the aryl group include a phenyl group, a toryl group and a naphthyl group, and the alkoxycarbonyl group includes 2 to 20 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, ethoxyethoxycarbonyl group, octyloxycarbonyl group and dodecyloxycarbonyl group There is an alkoxycarbonyl group which has.
Examples of the acyloxy group include acyloxy groups having 2 to 20 carbon atoms, such as an acetoxy group, a propanoyloxy group, an octanoyloxy group, and a benzoyloxy group.
Examples of the aralkyl group include aralkyl groups having 7 to 15 carbon atoms such as substituted or unsubstituted benzyl groups and substituted or unsubstituted phenethyl groups. Preferred examples of the substituent for the aralkyl group are the same as those described above.
In the substituents R ₃₁ to R ₅₁ , two substituents in each group of R ₃₁ to R ₃₅ and R ₃₆ to R ₄₂ and R ₄₃ to R ₅₁ may be bonded to each other to form a carbon and / or a hetero atom. And an 8-component ring. The 5- to 8-component ring includes cyclohexane, pyridine, furan and pyrrolidine.
X and Y may each bind to other imido sulfonate compound residues to form a two- or three-molecule body. Examples of such other imido sulfonates include compounds represented by the formula (A-6) wherein X or Y is a monovalent group.
Examples of the alkylene group represented by X include linear and branched alkylene groups having 1 to 10 carbon atoms, and monocyclic or polycyclic alkylene groups which may contain heteroatoms. Examples of the linear or branched alkylene group include methylene group, ethylene group, propylene group and octylene group. As the substituent for the alkylene group, an alkoxy group, acyl group, formyl group, nitro group, acylamino group, sulfonylamino group, halogen atom, aryl group or alkoxycarbonyl group is preferable. Such alkoxy groups, acyl groups, nitro groups, acylamino groups, sulfonylamino groups, aryl groups and alkoxycarbonyl groups are the same as those described for R ₃₁ to R ₅₁ . Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.
Examples of the cyclic alkylene group include monocyclic cycloalkylene groups having 4 to 8 carbon atoms, such as cyclopentylene group and cyclohexylene group, and 5 to 15 such as 7-oxabicyclo [2,2,1] heptylene There is a polycyclic cycloalkylene group having a carbon atom. As the substituent for the cycloalkylene, an alkyl group, an alkoxy group, an acyl group, a nitro group, an acylamino group, a sulfonylamino group, an aryl group or an alkoxycarbonyl group having 1 to 4 carbon atoms is preferable. Such alkoxy groups, acyl groups, formyl groups, nitro groups, acylamino groups, sulfonylamino groups, halogen atoms, aryl groups and alkoxycarbonyl groups have the same meanings as those described for R ₃₁ to R ₅₁ . Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.
Examples of the arylene group include a phenylene group and a naphthylene group. The substituent for the arylene group is preferably an alkyl group, cycloalkyl group, alkoxy group, acyl group, formyl group, nitro group, acylamino group, sulfonylamino group, halogen atom, aryl group or alkoxycarbonyl group. Such alkyl, cycloalkyl, alkoxy, acyl, formyl, nitro, acylamino, sulfonylamino, aryl and alkoxycarbonyl groups have the same meanings as described for R ₃₁ to R ₅₁ . Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.
Examples of the alkenylene group include an alkenylene group having 2 to 4 carbon atoms such as an ethenylene group and a butenylene group. As the substituent for the alkenylene group, an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, a formyl group, a nitro group, an acylamino group, a sulfonylamino group, an aryl group and an alkoxycarbonyl group are preferable. Such alkyl, cycloalkyl, alkoxy, acyl, formyl, nitro, acylamino, sulfonylamino, halogen, aryl or alkoxycarbonyl groups have the same meanings as described for R ₃₁ to R ₅₁ . Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.
Examples of the cyclic alkenylene group include monocyclic cycloalkenylene groups having 4 to 8 carbon atoms, such as cyclopentenylene groups and cyclohexenylene groups, and 7-oxabicyclo [2,2,1] heptenylene and nord There is a polycyclic cycloalkenylene group having 5 to 15 carbon atoms such as bonylene.
Examples of the aralkylene group include tolylene group and xylene group. Examples of substituents thereon include the substituents described for the arylene group.
Although detailed examples (A-6-1) to (A-6-49) represented by formula (A-6) are shown below, the present invention is by no means limited to these examples.


The compound represented by formula (A-6) is G.F. The method described in Jaubert, Ber., 28, 360 (1895), D.E. Ames et al., J. Chem. Soc., 3518 (1955) or M.A. Stolberg et al., J. Am. Chem. N-hydroxyimide compounds prepared by the methods described in Soc., 79, 2615 (1957) and described, for example, in L. Bauer et al., J. Org. It may also be synthesized from sulfonic acid chloride prepared under basic conditions according to the method described in Chem., 24, 1294 (1959).
Photo-acid generator represented by formula (A-7)
In formula (A-7), Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted aryl group.
Examples of the aryl group include a phenyl group, a toryl group and a naphthyl group. Substituents for the aryl groups include alkyl groups, cycloalkyl groups, alkoxy groups, acyl groups, formyl groups, nitro groups, acylamino groups, sulfonylamino groups, halogen atoms, aryl groups or alkoxycarbonyl groups. Such alkyl group, cycloalkyl group, alkoxy group, acyl group, formyl group, nitro group, acylamino group, sulfonylamino group, halogen atom, aryl group or alkoxycarbonyl group has the same meaning as described for R ₃₁ to R ₅₁ . Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.
Although the specific example of the photo-acid generator represented by Formula (A-7) is shown below by (A-7-1)-(A-7-14), this invention is not limited only to this illustration at all.
The photo-acid generator represented by formula (A-7) is G.C. Denser, Jr. et al., the method described in Journal of Organic Chemistry, 31, 3418-3419 (1966), T.P. It may also be synthesized by the method described in Hilditch, Journal of the Chemical Society, 93, 1524-1527 (1908) or by the method described in O. Hinsberg, Berichte der Deutschen Chemischen Gesellscahft, 49, 2593-2594 (1918). More specifically, a method for synthesizing sulfonic acid represented by formula (a) using cobalt sulfate in aqueous sulfuric acid solution, and a method for synthesizing sulfonic acid represented by formula (b) using ethyl acid acetate (xanthate) Alternatively, a method of synthesizing sulfonic acid represented by formula (a) and chloride sulfonic acid represented by formula (b) under a basic state may be used.
Ar ₁ -SO ₂ H (a)
Ar ₂ -SO ₂ Cl (b)
(Wherein Ar ₁ and Ar ₂ have the same meanings as defined in formula (A-7)).
In this invention, the photo-acid generator represented by Formula (A-1)-(A-5) is more preferable among the photo-acid generator represented by Formula (A-1)-(A-7). By using these, better resolution and sensitivity can be obtained.
The content of the compound represented by any one of formulas (A-1) to (A-7) in the composition is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, based on the solids content of the whole composition. 1-7 weight% is very preferable.
In the compositions of the present invention, organic base compounds may be used. By using such compounds, storage stability is improved and line width changes due to PED are more preferably reduced.
Preferred examples of the organic base compound which can be used in the present invention include compounds having a higher basicity than phenol. In particular, nitrogen-containing hot air compounds are preferred.
Examples of the preferable chemical environment include structures represented by formulas (A) to (E).
(In this case, if R ²⁵¹ and R ²⁵² may be bonded to each other to form a ring, R ²⁵⁰ , R ²⁵¹ and R ²⁵² may be the same or different, each hydrogen atom, an alkyl group having 1 to 6 carbon atoms, Aminoamino groups having 1 to 6 carbon atoms, hydroxyalkyl groups having 1 to 6 carbon atoms, or substituted or unsubstituted aryl groups having 6 to 20 carbon atoms;
(Wherein, R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ may be the same or different, each representing an alkyl group having 1 to 6 carbon atoms).
Nitrogen-containing cyclic compounds (also called "cyclic amine compounds") and nitrogen-containing base compounds having two or more nitrogen atoms which differ in chemical environment in one molecule are more preferred compounds.
The cyclic amine compound having a polycyclic structure is preferable. Specific examples of the cyclic amine compound include compounds represented by the following formula (F).
Here, Y and Z each independently represent a linear, branched or cyclic alkylene group which may contain a hetero atom or may be substituted.
Examples of the hetero atom include nitrogen atom, sulfur atom and oxygen atom. The alkylene group having 2 to 10 carbon atoms is preferable, but the alkylene group having 2 to 5 carbon atoms is more preferable. Examples of the substituent for the alkylene group include an alkyl group having 1 to 6 carbon atoms, an aryl group or alkenyl group having 1 to 6 carbon atoms, a halogen atom and a halogen-substituted alkyl group. In addition, detailed examples of the compound represented by formula (F) include the compounds shown below:
Of these, 1,8-diazabicyclo [5,4,0] undeca-7-ene and 1,5-diazabicyclo [4,3,0] nona-5-ene are more preferred.
Preferred are compounds having an aminoalkyl group and a compound having a ring structure containing a nitrogen atom and a substituted or unsubstituted amino group with a nitrogen-containing base compound containing two or more nitrogen atoms having different chemical environments in one molecule. Preferred examples of the compound include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, Unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted Piperazine, substituted or unsubstituted aminomorpholine and substituted or unsubstituted aminoalkylmorpholine. As the substituent, amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxy group and cyano group are preferable.
Of these, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine , 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methyl Pyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperazine, 4-amino- 2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, 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-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) mol Lin, trimethylamine, imidazole and triphenyl imidazole and methyl diphenyl is preferred than the imidazole. However, the present invention is by no means limited to these examples.
Such nitrogen-containing base compounds may be used alone or in combination. The content of the nitrogen-containing base compound used is generally 0.001 to 10 parts by weight based on 100 parts by weight of the present photosensitive resin composition (excluding the solvent), but is preferably 0.01 to 5 parts by weight. When the amount of use is less than 0.001 part by weight, the above-described effects cannot be obtained. On the other hand, when the amount of use exceeds 10 parts by weight, the sensitivity decreases or the developability of the non-exposed areas tends to be reduced.
The chemically amplified positive resist composition of the present invention may further contain a compound having two or more phenol OH groups capable of accelerating solubility in a surfactant, dye, pigment, plasticizer, photo-sensitizer, developer, etc., if necessary.
It is preferable that the said photosensitive resin composition of this invention contains surfactant. Detailed examples thereof include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene steryl ether, polyoxyethylene cetyl ether and polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether and Polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenol ethers, polyoxyethylene-polyoxypropylene block copolymers, sorbitan monopalmitate, sorbitan monosterate, sorbitan monooleate, sorbitan trioleate and Sorbitan fatty acid esters such as sorbitan tristerate and polyoxyethylene sorbitan monolaurate. Nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monosterate, polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristerate; Eftop EF301, EF303, EF352 (New Akita Kasei Co., Ltd.) Megafac F171, F173, F176, F189, R08 (Dai Nippon Ink & Chemical Co., Ltd.), FLORAD FC430, FC431 (Sumimoto 3M Company), Asahiguard AG710, SURFLON Fluorine-based surfactants such as S-382, SC101, SC102, SC103, SC104, SC105, and SD106 (manufactured by Asahi Glass Co., Ltd.); Organosiloxane polymer KR341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-base or methacrylic acid-base (co) polymer POLYFLOW No. 75, No.95 (product of Kyoeisa Yushi Chemical Co., Ltd.) and TOROYSOL S-366 (Toroi Chemical company products).
Among these surfactants, fluorine-based or silicone-based surfactants are preferred from the viewpoint of reducing applicability and developing defects.
The amount of the surfactant is generally 0.01 to 2% by weight, based on the total solids of the composition of the present invention, but 0.01 to 1% by weight is preferable.
Such surfactants may be used alone or in the form of a combination of two or more thereof.
In addition, the photo-acid generator in which the spectroscopic sensitizer described below may be added to the composition in a region having a wavelength longer than that of the far ultraviolet which is not absorbed at all. This allows the chemically amplified positive resist of the present invention to sensitivity to the g-line. Examples of suitable spectroscopic sensitizers include benzophenone, p, p'-tetramethyldiaminobenzophenone, p, p'-tetraethylethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, Anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2- Nitrofluorenone, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, peak Lamides, anthraquinones, 2-ethyl atlaquinones, 2-tert-butylanthraquinones, 1,2-benzanthraquinones, 3-methyl-1, 3-diaza-1,9-benzanthraquinones, dibenzalac Tones, 1,2-naphthoquinone, 3,3'-carbonylbis (5,7-dimethoxycarbonylcoumarin) and coronene, but the present invention is by no means limited to this example.
An example of a compound having two or more phenol OH groups capable of accelerating solubility in a developer is a polyhydroxy compound. Preferred examples of the polyhydroxy compound include phenol, resorcinol, phloroglucine, phlorogluside, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzo Penon, , ', '-Tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane and 1,1'-bis ( 4-hydroxyphenyl) cyclohexane.
The chemically amplified positive photoresist composition of the present invention is dissolved in a solvent capable of dissolving the above-described components and then applied onto a substrate. Examples of such solvents that may be used include ethylenedichloride, cyclohexanone, cyclopentanone, 2-heptanone, Butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether. Ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxy pro Cypionate, ethyl ethoxy propionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidine and tetrahydrofuran. Such solvents are used alone or in combination.
The chemically amplified positive resist composition is applied to a substrate used in the manufacture of a precision integrated circuit device by a suitable coating method such as a spinner or an applicator, then exposed through a predetermined mask, baked, and developed to produce a good resist. A film can be obtained.
Examples of the developer for the chemically amplified positive resist composition of the present invention include, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium phosphate, sodium transition silicate, and water-soluble ammonia, n-amine and n-. Primary amines such as propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, form Amides such as amides and acetamides, tetramethylammonium hydroxide, triethyl (2-hydroxyethyl) ammonium hydroxide, tetraethylammonium hydroxide, tributylmethylammonium hydroxide, tetraethanolammonium hydroxide, methyltriethanolammonium hydroxide, benzylmethyldi Ethanol ammonium, benzyldimethylethanol ammonium hydroxide, benzyl triethanol ammonium hydroxide Quaternary amines such as rapropylammonium and tetrabutylammonium hydroxide and cyclic amines such as pyrrole and piperidine.
Example
Although the present invention has been described in greater detail below, the present invention is not limited to these examples.
Resin, photoacid generator, organic base, surfactant used in the examples
In the synthesis of the resin of the present invention, acetalization can be carried out by either a method using vinyl ether or acetal exchange using alcohol and alkyl vinyl ether.
Synthesis Example I-1 Synthesis of Vinyl Ether
Ethyl vinyl ether was mixed with phenethyl alcohol and mercury acetate was added thereto. The mixture was stirred at room temperature for 12 hours, extracted and washed with ethyl acetate and water. The extract was distilled off under reduced pressure to obtain phenethyl vinyl ether (VII-1) as a target.
Synthesis Example I-2 Synthesis of Vinyl Ether
Ethyl vinyl ether was mixed with phenethyl alcohol and the palladium-1,10-petanthroline complex was mixed there. The mixture was stirred at room temperature for 20 hours, extracted and washed with ethyl acetate and water. The extract was distilled off under reduced pressure to obtain phenethyl vinyl ether (VII-1) as a target.
Synthesis Example 1-3 Synthesis of Vinyl Ether
2-Chloroethyl vinyl ether was added to a THF solution of phenylmagnesium bromide and phenyl lithium. The mixture was heated at reflux for 16 h, extracted and washed with ethyl acetate and water. The extract was distilled off under reduced pressure to obtain phenethyl vinyl ether (VII-1) as a target.
Synthesis Example I-4 ~ I-10
Vinyl ether (X-2) to (X-6) were obtained by appropriately selecting the method used in Synthesis Example I-1.
Synthesis Example II-1
120 ml of 32.4 g (0.2 mol) of p-acetoxy styrene was dissolved in butyl acetate and stirred in a nitrogen atmosphere three times every 2.5 hours, while 0.033 g of azobisisobutyronitrile (AIBN) was added thereto. ) Was added at 80 ° C. In order to carry out the polymerization reaction, the stirring was further continued for 5 hours. The reaction solution was immersed in 1.200 ml of hexane, and white resin precipitated. The obtained resin was dried and dissolved in 150 ml of methanol, and an aqueous solution (7.7 g (0.19 mol) of sodium hydroxide / 50 ml of water) was added thereto. The mixed aqueous solution was hydrolyzed by heating under reflux for 3 hours, and then diluted by adding 200 ml of water, neutralized with hydrochloric acid to precipitate a white resin. The resin was separated by filtration, washed with water and dried. The resulting solution was dissolved in 200 ml of tetrahydrofuran. The resulting resin was added dropwise to 5 L of high purity water with vigorous stirring to reprecipitate the resin. The resin obtained by repeating this reprecipitation operation three times was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain poly (p-hydroxystyrene) alkali-soluble resin R-1.
The weight average molecular weight of this resin was 15,000.
Synthesis Example II-2
35.25 g (0.2 mole) of p-tert-butoxystyrene monomer and 5.21 g (0.05 mole) of t-Bu styrene monomer were dehydrated and distilled-purified in a conventional manner to dissolve in 100 ml of tetrahydrofuran. To the resultant solution, 0.033 g of azobisisobutyronitrile (AIBN) was added at 80 DEG C while stirring three times every 2.5 hours in a nitrogen atmosphere. In order to carry out the polymerization reaction, the stirring was further continued for 5 hours. The reaction solution was immersed in 1,200 ml of hexane, and white resin precipitated. The obtained resin was dried and dissolved in 150 ml of tetrahydrofuran.
4N hydrochloric acid was added thereto, and the mixed solution was then heated under reflux for 6 hours to undergo hydrolysis, followed by reprecipitation in 5 L of high purity water. The precipitated resin was separated by filtration, washed with water and dried. The resin was then dissolved in 200 ml of tetrahydrofuran. The resulting resin was added dropwise to 5 L of high purity water with vigorous stirring to reprecipitate the resin. The resin obtained by repeating this reprecipitation operation three times was dried in a vacuum drier at 120 ° C. for 12 hours to obtain a poly (p-hydroxystyrene / t-butylstyrene) copolymer alkali-soluble resin R-2.
The weight average molecular weight of this resin was 12,000.
Synthesis Example II-3
Poly (p-hydroxystyrene) (VP8000) from Nippon Soda Company was used as alkali-soluble resin R-3. The weight average molecular weight of this resin was 9,800.
Synthesis Example III-1
20 g listed in Synthesis Example II-3
Alkali-Soluble Resin R-3
Propylene Glycol Monoethyl Ether Acetate 80ml
(PGMEA)
It was dissolved in the flask and distilled under reduced pressure to remove water and PGMEA by azeotropic distillation.
After confirming that the water content was satisfactorily reduced, 7.0 g of vinyl ether X-1 and 50 mg of p-toluenesulfonic acid obtained in Synthesis Example I-1 were added and stirred at room temperature for 1 hour, followed by Triethylamine was added to the reaction to terminate the reaction.
Ethyl acetate was added to the reaction solution, washed with water once more, and then ethyl acetate, water and azeotropic PGMEA were removed by distillation under reduced pressure to give alkali-soluble resin B-1 having a specific substituent according to the present invention. Got it. The weight average molecular weight of the obtained resin was 11,000.
Synthesis Example III-2
20 g obtained in Synthesis Example II-3
Alkali-Soluble Resin R-3
Propylene Glycol Monomethyl Ether Acetate 80ml
(PGMEA)
This was dissolved in a flask, distilled under reduced pressure to remove water and PGMEA by azeotropic distillation.
After confirming that the water content was satisfactorily reduced, 7.0 g of phenethyl alcohol, 6.5 g of t-butyl vinyl ether and 50 mg of p-toluenesulfonic acid were added and stirred at room temperature for 1 hour, where triethyl was added. The amine was added and the reaction terminated.
Ethyl acetate was added to the reaction solution, washed with water once more, and then ethyl acetate, water and azeotropic PGMEA were removed by distillation under reduced pressure to give alkali-soluble resin B-1 having a specific substituent according to the present invention. Got it. The weight average molecular weight of the obtained resin was 11,000.
Synthesis of Resin B-2 to B-24
Similarly, resins B-2 to B-12, which are resins having the specific substituents in the present invention, were prepared using the vinyl ether and alkali-soluble resins shown in Table 1 below. In addition, alkali-soluble resins B-13 to B-24 were prepared by synthesizing the resin using the vinyl ether and alkali-soluble resin shown in Table 1, and 1.5 g of pyridine and 1.5 g of acetic anhydride were added thereto. The contents were stirred at room temperature for 1 hour.
SuzyUsed vinyl etherMain polymerUsed acid anhydride B-1X-1R-3none B-2X-2R-3none B-3X-3R-3none B-4X-4R-3none B-5X-5R-3none B-6X-6R-3none B-7X-1R-2none B-8X-2R-2none B-9X-3R-2none B-10X-4R-2none B-11X-5R-2none B-12X-6R-2none B-13X-1R-3Acetic anhydride B-14X-2R-3Acetic anhydride B-15X-3R-3Acetic anhydride B-16X-4R-3Acetic anhydride B-17X-5R-3Acetic anhydride B-18X-6R-3Acetic anhydride B-19X-1R-1Acetic anhydride B-20X-2R-1Acetic anhydride B-21X-3R-1Acetic anhydride B-22X-4R-1Acetic anhydride B-23X-5R-1Acetic anhydride B-24X-6R-1Acetic anhydride
Resins B-2 to B-24 can also be prepared by the acetal exchange method described above from the corresponding alcohols and t-butylvinyl ethers.
Synthesis Example IV-1
Resin C-1 was obtained using an alkali-soluble resin shown in Table 2 and ethyl vinyl ether (Y-1) shown below.
SuzyUsed vinyl etherMain polymer C-1Y-1R-3
Poly (p-1-benzoxy-1-methylethoxystyrene / p-hydroxystyrene / p-tert-butoxystyrene) described in JP-A-8-123032 was used as Resin C-2.
Synthesis Example V-1 Synthesis of D-1
19.9 g (0.030 mol) of chemically useful triarylsulfonium Cl salt (50% aqueous solution of triphenylsulfonium chloride from Fluka), triphenylsulfonium, 4,4'-bis (diphenyl-sulfonio ) Diphenyl sulfide and the like were dissolved in 200 ml of ion-exchanged water. As a result, 400 ml of an ion exchange aqueous solution containing 10.5 g (0.030 mol) of Na salt of hard (side chain type) dodecylbenzenesulfonic acid having the structure shown below was added at room temperature with stirring. .
The precipitated viscous solids were separated by decantation and washed with 1 L of ion exchanged water.
The obtained viscous solid was dissolved in 100 ml of acetone and poured into 500 ml of ion-exchanged water while stirring to recrystallize it. The precipitate was dried at 50 ° C. under vacuum to give 15.5 g of a glassy solid. NMR measurements revealed that this solid was the target photo-acid generator (D-1), which was the main mixture.
Synthesis Example V-2 Synthesis of D-2 (A-1-56 exemplified above)
68 g (0.174 mole) of triphenylsulfonium iodide and 42.5 g (0.183 mole) of silver oxide were dissolved in 500 mL of methanol and stirred at room temperature for 5 hours. Subsequently, the insolubles were separated by filtration and 59.4 g (0.209 mol) of triisopropylbenzenesulfonic acid were added. The resulting solution was stirred at room temperature for 3 hours and condensed into a powder. The powder was washed with water and recrystallized with ethyl acetate / acetone = 6/4 to obtain 50 g of a photo-acid generator (D-2) as a target product. The structure was confirmed by NMR.
Synthesis Example V-3 Synthesis of D-3 (A-1-63 exemplified above)
7 g of phosphorus pentoxite and 70 g of methanesulfonic acid were mixed with stirring, dissolved, and stirred at room temperature. 25 g (0.124 mol) of diphenyl sulfoxide and 20.4 g (0.136 mol) of n-butoxybenzene were added thereto while stirring, followed by further stirring at 50 ° C for 4 hours. The obtained reaction solution was poured into 500 mL of ice water, washed twice with 150 mL of toluene, and slightly alkaline with tetramethylammonium hydroxide. Then, butoxyphenyl diphenylsulfonium methane sulfonate of an aqueous solution was obtained.
Thereto, 1,000 ml of ethyl acetate was added and stirred, and the solution obtained by adding butanol to 26 g (0.14 mol) of 2-sulfobenzoic acid cyclic anhydride was added and stirred. The resulting solution was separated into an organic layer and an aqueous layer by washing it twice with 500 ml of 10% tetramethylammonium hydroxide in an aqueous solution, and then further washed three times with water. The organic layer was dried and condensed to obtain a photo-acid generator (D-3) as a target product.
Synthesis Example V-4: Synthesis of D-4 (A-2-57 illustrated above)
1) Synthesis of Tetramethylammonium Pentafluorobenzene Sulfonate
25 g of pentafluorobenzenesulfonyl chloride was dissolved in 100 ml of methanol under ice cooling, and 100 g of 25% aqueous tetramethylammonium hydroxide solution was slowly added thereto. The resultant solution was stirred at room temperature for 3 hours to obtain a tetramethylammonium pentafluorobenzene sulfonate solution. This solution was used as a salt to ion exchange with a sulfonium salt or iodonium salt.
2) Synthesis of (4-t-amylphenyl) iodonium pentafluorobenzene sulfonate (D-4)
60 g of t-amylbenzene, 39.5 g of potassium iodate, 81 g of acetic anhydride and 170 ml of dichloromethane were mixed, and then 66.8 g of concentrated sulfuric acid was slowly added dropwise under ice cooling. The mixture was stirred for 2 hours under ice cooling, then stirred at room temperature for 10 hours, and 500 ml of water was added to the reaction solution under ice cooling. The resulting solution was extracted with dichloromethane, and the organic layer was washed with sodium bicarbonate and water and condensed to obtain di (4-t-amylphenyl) iodium sulfate. This sulfate was added to a solution containing excess tetramethylammonium pentafluorobenzene sulfonate. After adding 500 ml of water thereto, the solution was extracted with dichloromethane and the organic layer was washed with 5% aqueous solution of tetramethylammonium hydroxide and water, then condensed to di (4-t-amylphenyl) iodium penta. Fluorobenzene sulfonate (D-4) was obtained.
Synthesis Example V-5: Synthesis of D-5 (A-1-60 illustrated above)
50 g of diphenyl sulfoxide was dissolved in 800 ml of benzene and 200 g of ammonium chloride was added thereto and refluxed for 24 hours. The reaction solution was slowly poured into 2 L of ice water, and 400 ml of concentrated hydrochloric acid was added thereto and heated at 70 ° C. for 10 minutes. This aqueous solution was washed with 500 ml of ethyl acetate and filtered. A solution obtained by dissolving 200 g of ammonium iodide was added thereto. The precipitated powder was collected by filtration and washed with water. It was further dried by washing with ethyl acetate. Thus, 70 g of triphenylsulfonium iodide was obtained.
30.5 g of triphenylsulfonium iodide was dissolved in 1,000 ml of methanol, and 19.1 g of silver oxide was added to the solution and stirred at room temperature for 4 hours. The resulting solution was filtered, and thereto was added a solution containing excess tetramethylammonium pentafluorobenzene sulfonate. The reaction solution was concentrated and dissolved in 500 ml of dichloromethane, and the resultant solution was washed with 5% aqueous tetramethylammonium hydroxide solution and water. The organic layer was dried over anhydrous sodium sulfate and then condensed. As a result, triphenylsulfonium pentafluorobenzene sulfonate (D-5) was obtained.
Synthesis Example V-6 Synthesis of D-6
50 g of triarylsulfonium chloride (Fluka, 50% aqueous solution of triphenylsulfonium chloride) was dissolved in 500 ml of water, and a solution containing excess tetramethylammonium pentafluorobenzene sulfate was added thereto. , Oily substance precipitated. The supernatant was removed by decantation, the oily substance obtained was washed with water, and then dried to obtain triarylsulfonium pentafluorobenzene sulfonate (D-6) as a main mixture.
As the photo-acid generator D-7, 1-diazo-1-methylsulfonyl-4-phenylbutan-2-one described in JP-A-8-123032 was used.
The organic base used has the following structure (E-1), (E-2) or (E-3).
As the surfactant (F-1), Megafac R08 (manufactured by Dai-Nippon Ink & Chemical Co., Ltd.) was used.
As the surfactant (F-2), TOROYSOL S-366 (manufactured by Toroy Chemical Industries, Ltd.) was used.
Examples 1-22 and Comparative Examples 1-3
Preparation and Evaluation of Photosensitive Compositions
Each material shown in Table 3 dissolved 8 g of PGMEA (propylene glycol monoethyl ether acetate) and passed through a 0.2 μm filter to prepare a resist solution. The content of the surfactant was 0.0035 g. Each resist solution was applied onto the silicon flakes with a spin applicator and dried on a vacuum absorbing hotplate at 130 ° C. for 60 seconds to obtain a resist film having a thickness of 0.8 μm.
Suzy[The furtherance ratio of resin]Amount of resin (g)Photo-acid generatorAmount of photo-acid generator (g)Organic baseAmount of organic base (g)Surfactants Example 1B-120/10/702.0D-10.05E-20.001F-2 Example 2B-21/10/722.0D-10.05E-20.001F-1 Example 3B-320/10/702.0D-10.05E-30.001F-1 Example 4B-420/10/702.0D-10.05E-20.001F-1 Example 5B-518/10/722.0D-20.05E-10.001F-2 Example 6B-620/10/702.0D-30.05E-20.001F-1 Example 7B-115/7/782.0D-2 / D-30.05E-20.001F-2 Example 8B-215/7/782.0D-2 / D-30.05E-20.001F-1 Example 9B-315/7/782.0D-2 / D-30.05E-20.001F-1 Example 10B-417/7/252.0D-2 / D-30.05E-20.001F-2 Example 11B-517/7/252.0D-2 / D-30.05E-20.001F-1 Example 12B-615/7/782.0D-2 / D-30.05E-20.001F-1 Example 13B-118/10/722.0D-40.05E-20.001F-2 Example 14B-218/10/722.0D-50.05E-20.001F-2 Example 15B-320/10/702.0D-40.05E-30.001F-1 Example 16B-420/10/702.0D-50.05E-20.001F-1 Example 17B-518/10/722.0D-40.05E-20.001F-2 / F-1 Example 18B-618/10/722.0D-2 / D-40.05E-20.001F-2 / F-1 Example 19B-618/10/722.0D-2 / D-60.05E-2 / E-30.001F-2 Example 20B-618/10/722.0D-2 / D-50.05E-2 / E-30.001F-2 Example 21B-618/10/722.0D-4 / D-50.05E-30.001F-1 Example 22B-618/10/722.0D-2 / D-30.05E-1 / E-20.001F-1 Example 23B-218/10/722.0D-60.05E-30.001F-1 Example 24B-1215/7/782.0D-10.05E-20.001F-1 Example 25B-1215/7/782.0D-30.05E-20.001F-2 Example 26B-1215/7/782.0D-40.05E-20.001F-2 Example 27B-1215/7/782.0D-50.05E-30.001F-1 Example 28B-1215/7/782.0D-60.05E-20.001F-1 Example 29B-218/10/722.0D-2 / D-30.05E-20.001F-2 / F-1 Example 30B-1215/7/782.0D-2 / D-30.05E-20.001F-2 / F-1 Example 31B-218/10/722.0D-2 / D-30.05E-2 / E-30.001F-2 Example 32B-1215/7/782.0D-2 / D-30.05E-2 / E-30.001F-2 Example 33B-218/10/722.0D-2 / D-30.05E-30.001F-1 Example 34B-1215/7/782.0D-2 / D-30.05E-2 / E-30.001F-1 Comparative Example 1C-140/0/602.0D-20.05E-20.001- Comparative Example 2C-230/10/602.0D-70.05E-20.001- Comparative Example 3C-140/0/602.0D-70.05E-20.001-
In Table 3, the weight ratios of D-2 / D-3, D-2 / D-4, D-2 / D-6, D-2 / D-5, and D-4 / D-5 are 50, respectively. It was: 50.
The weight ratio of F-2 / F-1 used in Examples 17 and 18 was 50:50.
The weight ratio of E-2 / E-3 used in Examples 19 and 20 was 50:50.
The weight ratio of E-1 / E-2 used in Example 22 was 50:50.
These ratios are the same as in Table 5.
Each resist film was exposed using 248 nm KrF excimer laser stepper (NA = 0.45). After exposure, the silicon flakes coated with the resist film thereon were heated on a hot plate at 100 ° C. for 60 seconds, and then immediately immersed in an aqueous solution of 0.26 N tetramethylammonium hydroxide (TMAH) for 60 seconds, and for 30 seconds. Rinse with water and dry. The silicon flake pattern thus obtained was observed with a scanning electron microscope to evaluate the performance of the resist. The results are shown in Table 4.
The resolution shows the critical resolution at the exposure dose required to reproduce the mask pattern of 0.30-µm lines and spaces.
Each of the resist patterns was observed through an optical microscope or SEM to evaluate surface roughness. Very clean surfaces were evaluated as "A", clean surfaces as "B", and rough surfaces as "C".
The development defect was evaluated by applying a resist solution on 6-inch flakes to count the number of stains corresponding to the development defect. A very small number of developing defects was evaluated as "A", a small number of developing defects was evaluated as "B", and a large number of developing defects was evaluated as "C".
Sensitivity (mj / ㎠)Resolution (μm)Surface roughnessPhenomenon Example 1200.24AA Example 2210.25AA Example 3210.25AA Example 4200.25AA Example 5190.26AA Example 6220.24AA Example 7210.25AA Example 8210.24AA Example 9210.25AA Example 10220.24AA Example 11220.24AA Example 12230.24AA Example 13190.24AA Example 14190.25AA Example 15200.25AA Example 16210.25AA Example 17200.24AA Example 18210.25AA Example 19220.24AA Example 20220.24AA Example 21210.25AA Example 22220.24AA Comparative Example 1200.28CC Comparative Example 2220.29CC Comparative Example 3280.28CC
As is clear from the results in Table 4, in the case of the positive photoresist composition of the example according to the present invention, satisfactory results have been obtained. In contrast, in the case of the photoresist composition of the example, the surface roughness and the development defect are detailed. A satisfactory result was not obtained.
Examples 23-56 and Comparative Examples 4-6
As shown in Table 5 below, in order to produce a resist film having 0.8 mu m, except that each resin having a structural unit represented by formula (I), (II) and (III) was produced Each liquid resist was obtained in the same manner as in 1 to 22.
The prepared resist film was evaluated for sensitivity, resolution, surface roughness and development defects, and the results are shown in Table 6 below.
SuzyComposition ratio of resinAmount of resin (g)Photo-acid generatorAmount of photo-acid generator (g)Organic baseAmount of organic base (g)Surfactants Example 23B-1320/10/702.0D-10.05E-20.001F-2 Example 24B-1418/10/722.0D-10.05E-20.001F-1 Example 25B-1520/10/702.0D-10.05E-30.001F-1 Example 26B-1620/10/702.0D-10.05E-20.001F-1 Example 27B-1718/10/722.0D-20.05E-10.001F-2 Example 28B-1820/10/702.0D-30.05E-20.001F-1 Example 29B-715/7/82.0D-10.05E-30.001F-1 Example 30B-815/7/82.0D-20.05E-2 / E-30.001F-2 Example 31B-915/7/82.0D-20.05E-30.001F-1 Example 32B-1017/7/252.0D-30.05E-2 / E-30.001F-1 Example 33B-1117/7/252.0D-10.05E-20.001F-1 Example 34B-1215/7/782.0D-20.05E-2 / E-30.001F-1 Example 35B-1918/10/722.0D-30.05E-20.001F-2 Example 36B-2018/10/722.0D-10.05E-20.001F-1 Example 37B-2120/10/702.0D-20.05E-30.001F-1 Example 38B-2220/10/702.0D-30.05E-20.001F-2 Example 39B-2318/10/722.0D-10.05E-30.001F-1 Example 40B-2418/10/722.0D-10.05E-20.001F-1 Example 41B-1418/10/722.0D-20.05E-20.001F-1 Example 42B-1418/10/722.0D-30.05E-20.001F-2 Example 43B-1418/10/722.0D-40.05E-20.001F-1 Example 44B-1418/10/722.0D-50.05E-20.001F-1 Example 45B-1418/10/722.0D-60.05E-30.001F-1 Example 46B-1215/7/782.0D-10.05E-20.001F-1 Example 47B-1215/7/782.0D-30.05E-20.001F-2 Example 48B-1215/7/782.0D-40.05E-20.001F-2 Example 49B-1215/7/782.0D-50.05E-30.001F-1 Example 50B-1215/7/782.0D-60.05E-20.001F-1 Example 51B-1418/10/722.0D-2 / D-30.05E-20.001F-2 / F-1 Example 52B-1215/7/782.0D-2 / D-30.05E-20.001F-2 / F-1 Example 53B-1418/10/722.0D-2 / D-30.05E-2 / E-30.001F-2 Example 54B-1215/7/782.0D-2 / D-30.05E-2 / E-30.001F-2 Example 55B-1418/10/722.0D-2 / D-30.05E-30.001F-1 Example 56B-1215/7/782.0D-2 / D-30.05E-2 / E-30.001F-1 Comparative Example 4C-140/0/602.0D-20.05E-20.001- Comparative Example 5C-230/10/602.0D-70.05E-20.001- Comparative Example 6C-340/0/602.0D-70.05E-20.001-
Sensitivity (mj / ㎠)Resolution (μm)Surface roughnessPhenomenon Example 23190.24AA Example 24210.25AA Example 25220.25AA Example 26200.25AA Example 27200.26AA Example 28220.25AA Example 29230.24AA Example 30220.24AA Example 31210.25AA Example 32230.24AA Example 33210.24AA Example 34200.24AA Example 35210.25AA Example 36220.24AA Example 37210.24AA Example 38240.24AA Example 39220.24AA Example 40200.24AA Example 41220.24AA Example 42210.24AA Example 42210.25AA Example 43210.26AA Example 44220.25AA Example 45220.25AA Example 46200.24AA Example 47190.24AA Example 48190.25AA Example 49200.25AA Example 50210.25AA Example 51200.24AA Example 52210.25AA Example 53220.24AA Example 54220.24AA Example 55210.25AA Example 56220.24AA Comparative Example 4200.28CC Comparative Example 5220.29CC Comparative Example 6280.28CC
From the results shown in Table 6, the positive photoresist composition of the present invention showed better surface roughness and development defects and satisfactory results, while the positive composition of the comparative example specifically satisfied the roughness and development defects of the resist surface. It can be seen that it shows undesired results.
There is provided a chemically amplified positive photoresist composition having high sensitivity and high resolution and improved surface roughness and development defects.
Although the present invention has been described in detail with reference to the detailed embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention.

权利要求:
Claims (11)
[1" claim-type="Currently amended] A resin (a) having a structural unit represented by the following formula and capable of increasing solubility in an alkali-developing solution by decomposition by the action of an acid, and
A positive photoresist composition comprising a compound (b) capable of decomposing upon irradiation with actinic radiation or radiation to generate an acid:

Here, R1 and R2 may be the same or different, each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R3 and R4 may be the same or different, each may have a hydrogen atom or a substituent , Branched or cyclic alkyl group, R5 represents a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent or an aralkyl group which may have a substituent, and m is The integer of 1-20 is shown and n represents the integer of 0-5.
[2" claim-type="Currently amended] A resin (a) having structural units represented by the following formulas (I), (II) and (III), which can be decomposed by the action of an acid to increase solubility in an alkaline developer; and
A positive photoresist composition comprising a compound (b) capable of generating an acid by irradiation with actinic radiation or radiation:

Wherein R21 represents a hydrogen atom or a methyl group, R22 represents a group that cannot be decomposed by the action of an acid, R23 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an acyl group or an acyloxy group , n represents an integer of 1 to 3, and W represents a group represented by the following formula:

Here, R ₁ and R ₂ may be the same or different, each is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R3 and R4 may be the same or different, each of which may have a hydrogen atom or a substituent, linear, Branched or cyclic alkyl group, R5 represents a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, and m represents 1-20 An integer is displayed and n represents the integer of 0-5.
[3" claim-type="Currently amended] The compound (b) according to claim 1, wherein the compound (b) capable of generating an acid by irradiation with actinic rays or radiation is represented by the following formulas (A-1), (A-2), (A-3), (A-4), (A A positive photoresist composition, characterized by at least one compound capable of generating sulfonic acid by irradiation of actinic rays or radiation, represented by A-5), (A-6) and (A-7):

Wherein R ₁ to R ₅ may be the same or different, and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom or -SR _{6 in} which R ₆ is an alkyl group or an aryl group, and X ^- is 8 At least one group selected from the group consisting of branched or cyclic alkyl or alkoxy groups having 2 or more carbon atoms, at least 2 selected from the group consisting of linear, branched or cyclic alkyl or alkoxy groups having 4 to 7 carbon atoms At least three groups selected from the group consisting of linear, branched alkyl or alkoxy groups having 1 to 3 carbon atoms, linear or branched ester groups having 1 to 5 halogen atoms or 1 to 10 carbon atoms Anion of benzene sulfonic acid, naphthalene sulfonic acid or anthracene sulfonic acid having

Wherein R ₇ to R ₁₀ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group or a halogen atom, and X ⁻ is branched or cyclic having 8 or more carbon atoms At least one group selected from the group consisting of alkyl or alkoxy groups, linear, branched or cyclic alkyl groups having from 4 to 7 carbon atoms, at least two groups selected from the group consisting of alkoxy groups, linear having from 1 to 3 carbon atoms Or benzene sulfonic acid, naphthalene sulfonic acid or anthracene sulfonic acid having at least three groups selected from the group consisting of branched alkyl or alkoxy groups, linear or branched ester groups having 1 to 5 halogen atoms or 1 to 10 carbon atoms An anion of phonic acid is indicated, and m, n, p and q each represent an integer of 1 to 3;

Wherein R ₁₁ to R ₁₃ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom or —SR ₆ , and X ⁻ has the same meaning as defined above 1, m and n may be the same or different, and each represents an integer of 1 to 3, and when 1, m and n are 2 or 3, two or more including carbon rings, heterocycles or aromatic rings Two of three R ₁₁ , R _12, or R ₁₃ groups combine to form a ring of 5-8 elements.

Wherein R ₁₄ to R ₁₆ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom or —SR ₆ , and X ⁻ has the same meaning as defined above 1, m and n may be the same or different, and each represents an integer of 1 to 3, and when 1, m and n are 2 or 3, two or more including carbon rings, heterocycles or aromatic rings Two of the three R ₁₄ , R ₁₅ or R ₁₆ groups combine to form a ring of 5 to 8 elements.

Wherein Y is a linear, branched or cyclic alkyl group which may be substituted, an aralkyl group which may be substituted, or

Wherein R ₃₁ to R ₅₁ may be the same or different, each of which is a halogen atom, a linear, branched or cyclic alkyl, alkoxy, acyl, acylamino, sulfonylamino, aryl, acyloxy, If aralkyl or alkoxycarbonyl group, a formyl group, a nitro group, a chlorine atom, a bromine atom, an iodine atom, show a hydroxyl group or a cyano group, and if, Y is other may already be combined also with the residue of a sulfonate compound, R ₃₁ Two of R ₃₅ , two R ₃₆ to R ₄₂ , or two R ₄₃ to R ₅₁ may combine with each other to form a 5-, 6-, 7-, or 8-component ring of carbon and / or heteroatoms; Or if X is to be bonded to other imido sulfonate compound residues, then X may be a linear or branched alkylene group which may have substituents, monocyclic which may have substituents or contain heteroatoms. All The display of the alkylene group, which may have a substituent of the linear or branched alkylene group, may be substituted or a hetero atom-containing monocyclic or polycyclic alkenylene group which may be substituted or an alkenylene group which; And
Ar ₁ -SO ₂ -SO ₂ -Ar ₂ (A-7)
Here, Ar ₁ and Ar ₂ may be the same or different, each represents a substituted or unsubstituted aryl group.
[4" claim-type="Currently amended] The positive photoresist composition according to claim 1, further comprising a cyclic amine compound.
[5" claim-type="Currently amended] The positive photoresist composition of claim 1, further comprising at least one of a fluorine-based surfactant and a silicone-based surfactant.
[6" claim-type="Currently amended] The positive photoresist composition according to claim 1, further comprising a compound which is decomposed by the action of an acid to increase solubility in an alkaline developer.
[7" claim-type="Currently amended] A positive photoresist composition according to claim 2, wherein the ratios of the structural formulas (I), (II) and (III) satisfy the following conditions (1) to (4):
(1) 0.10 <(I) / ((I) + (II) + (III)) <0.25,
(2) 0.01 <(II) / ((I) + (II) + (III)) <0.15,
(3) (I)> (II), and
(4) 0.5 <(I) / ((I) + (II)) <0.85
(Here, (I), (II) and (III) represent the molar ratios of the structural units having groups represented by the formulas (I), (II) and (III), respectively).
[8" claim-type="Currently amended] The compound (b) according to claim 2, wherein the compound (b) capable of generating an acid by irradiation with actinic rays or radiation is represented by the following formulas (A-1), (A-2), (A-3), (A-4), (A The positive photoresist composition represented by A-5), (A-6) and (A-7), which is at least one compound capable of generating sulfonic acid by irradiation with actinic rays or radiation.

Wherein, R ₁ ~ R ₅ are the same or may be different, and each is hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom, or R ₆ is -SR display ₆ for displaying an alkyl or aryl, X ^- Is at least one group selected from the group consisting of branched or cyclic alkyl or alkoxy groups having 8 or more carbon atoms, selected from the group consisting of linear, branched or cyclic alkyl or alkoxy groups having 4 to 7 carbon atoms At least 2 selected from the group consisting of linear or branched alkyl or alkoxy groups having 1 to 3 carbon atoms, linear or branched ester groups having 1 to 5 halogen atoms or 1 to 10 carbon atoms Anion of benzene sulfonic acid, naphthalene sulfonic acid or anthracene sulfonic acid having two groups;

Wherein R ₇ to R ₁₀ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group or a halogen atom, and X ⁻ is branched or cyclic having 8 or more carbon atoms At least one group selected from the group consisting of alkyl or alkoxy groups, linear, branched or cyclic alkyl groups having from 4 to 7 carbon atoms, at least two groups selected from the group consisting of alkoxy groups, linear having from 1 to 3 carbon atoms Or benzene sulfonic acid, naphthalene sulfonic acid or anthracene sulfonic acid having at least three groups selected from the group consisting of branched alkyl or alkoxy groups, linear or branched ester groups having 1 to 5 halogen atoms or 1 to 10 carbon atoms An anion of phonic acid is indicated, and m, n, p and q each represent an integer of 1 to 3;

Wherein R ₁₁ to R ₁₃ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom or —SR ₆ , and R ₆ and X ⁻ are as defined above. Have the same meaning, and 1, m and n may be the same or different and each represent an integer of 1 to 3, where 1, m and n are 2 or 3, a carbon ring, a heterocyclic ring or an aromatic ring Two of two or three R ₁₁ , R ₁₂ or R ₁₃ groups, each containing, combine to form a ring of 5 to 8 elements;

Wherein R ₁₄ to R ₁₆ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom or —SR ₆ , and X ⁻ represents the same meaning as defined above 1, m and n may be the same or different, and each represents an integer of 1 to 3, and when 1, m and n are 2 or 3, two or more including carbon rings, heterocycles or aromatic rings Two of three R ₁₄ , R ₁₅ or R ₁₆ groups each combine to form a ring of 5-8 elements;

Wherein Y is a linear, branched or cyclic alkyl group which may be substituted, an aralkyl group which may be substituted, or

Is displayed.
Wherein R ₃₁ to R ₅₁ may be the same or different, and if Y may be combined with another imido sulfonate compound, each may be a halogen atom, a linear, branched or cyclic alkyl which may have substituents, Alkoxy, acyl, acylamino, sulfonylamino, aryl, acyloxy, aralkyl or alkoxycarbonyl group, formyl group, nitro group, chlorine atom, bromine atom, iodine atom, hydroxy group or cyano group, and R ₃₁ to R ₃₅ Two of them, two of R ₃₆ to R ₄₂ or two of R ₄₃ to R _{51 may} combine to form a 5-, 6-, 7- or 8-component ring of carbon and / or heteroatoms, If X may be combined with another imido sulfonate compound, then X may be a linear or branched alkylene group which may have substituents, monocyclic or polycyclic alkylene groups or substituents which may have substituents or contain heteroatoms. Go The linear or branched chain alkylene group is displayed, a substituted or which may contain a hetero atom monocyclic or polycyclic alkenylene group, an aryl group or aralkyl Killen which may be substituted, which may which may be substituted; And
Ar ₁ -SO ₂ -SO ₂ -Ar ₂ (A-7)
Here, Ar ₁ and Ar ₂ may be the same or different, each represents a substituted or unsubstituted aryl group.
[9" claim-type="Currently amended] The positive photoresist composition according to claim 2, further comprising a cyclic amine compound.
[10" claim-type="Currently amended] The positive photoresist composition according to claim 2, further comprising at least one of a fluorine-based surfactant and a silicone-based surfactant.
[11" claim-type="Currently amended] The positive photoresist composition according to claim 2, further comprising a compound which is decomposed by the action of an acid to increase solubility in an alkaline developer.

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同族专利:

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公开号 | 公开日

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JP3963625B2|2007-08-22|

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KR100621456B1|2006-09-13|

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JP2001249458A|2001-09-14|

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US6630280B1|2003-10-07|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
1999-02-24|Priority to JP4652499

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1999-02-24|Priority to JP99-46524

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1999-04-13|Priority to JP99-105485

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1999-04-13|Priority to JP10548599

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1999-10-20|Priority to JP29860899

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1999-10-20|Priority to JP99-298608

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1999-12-28|Priority to JP99-372757

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1999-12-28|Priority to JP37275799A

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2000-02-24|Application filed by 무네유키 가코우, 후지 샤신 필름 가부시기가이샤

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2000-12-26|Publication of KR20000076727A

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2006-09-13|Application granted

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2006-09-13|Publication of KR100621456B1

优先权:

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申请号 | 申请日 | 专利标题

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JP4652499|1999-02-24|

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JP99-46524|1999-02-24|

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JP99-105485|1999-04-13|

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JP10548599|1999-04-13|

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JP29860899|1999-10-20|

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JP99-298608|1999-10-20|

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JP99-372757|1999-12-28|

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JP37275799A|JP3963625B2|1999-02-24|1999-12-28|Positive photoresist composition|