JP2001215707A - Positive photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photoresist composition ensuring improved edge roughness of a resist pattern in the production of a semiconductor device and excellent in low temperature preservability. SOLUTION: The positive photoresist composition contains (A) a compound which generates an acid when irradiated with active light or radiation, (B) an acid decomposable siloxane having a specified structural unit and (C) a specified solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photoresist composition used for manufacturing semiconductor integrated circuit elements, masks for manufacturing integrated circuits, printed wiring boards, liquid crystal panels, and the like.

[0002]

2. Description of the Related Art As a pattern forming method for manufacturing electronic components such as a semiconductor device, a magnetic bubble memory, and an integrated circuit, a method utilizing a photoresist which is sensitive to ultraviolet light or visible light has been widely used. Have been. There are two types of photoresist: a negative type, in which the irradiated part is insoluble in the developer by light irradiation, and a positive type, in which the exposed part is solubilized.The negative type has higher sensitivity than the positive type and is necessary for wet etching. Until recently, photoresists occupied the mainstream because of their excellent adhesion to substrates and chemical resistance.

However, with the increase in density and integration of semiconductor devices and the like, the line width and spacing of patterns have become extremely small.
In addition, since dry etching has been adopted for etching the substrate, photoresists have been desired to have high resolution and high dry etching resistance,
At present, positive photoresists occupy the majority. In particular, among positive photoresists, sensitivity,
Because of its excellent resolution and dry etching resistance, for example, JC Strieta, Kodak Microelectronics Seminar Proceedings, p. 116 (1976) (JC Strieter, Kodak Micro)
electronics Seminar Proceedings, 116 (1976
) And the like, and an alkali-developing positive photoresist based on an alkali-soluble novolak resin is the mainstream of the current process.

However, in recent years, multifunctional electronic devices have been
As the sophistication increases, there is a strong demand for finer patterns to achieve higher densities and higher integration.

That is, since the vertical dimension of the integrated circuit is not much reduced as compared with the horizontal dimension of the integrated circuit, the ratio of the height to the width of the resist pattern has to be increased. For this reason, it has become more difficult to suppress the dimensional change of the resist pattern on a wafer having a complicated step structure as the pattern becomes finer. Further, in various types of exposure methods, there is a problem with the reduction of the minimum size. For example,
In light exposure, the interference effect of reflected light due to the step of the substrate has a great effect on dimensional accuracy, whereas in electron beam exposure, the proximity effect caused by backscattering of electrons causes the fine resist pattern The height to width ratio can no longer be increased.

[0006] It has been found that many of these problems are eliminated by using a multilayer resist system. For a description of multilayer resist systems, see Solid State Technology, 74 (1981) [Solid State Technolog
y, 74 (1981)], but many other studies on this system have been published. Generally, a multilayer resist method includes a three-layer resist method and a two-layer resist method. In the three-layer resist method, an organic flattening film is applied on a stepped substrate, an inorganic intermediate layer and a resist are stacked thereon, and the resist is patterned. Then, the inorganic intermediate layer is dry-etched using the resist as a mask. This is a method of patterning an organic flattening film by O2 RIE (reactive ion etching) using the inorganic intermediate layer as a mask. Basically, this method has been studied from an early stage because conventional techniques can be used, but the process is very complicated, or the organic film, the inorganic film, and the organic film have different three-layer physical properties. The problem is that cracks and pinholes are likely to occur in the intermediate layer due to the overlapping of the objects.

In contrast to the three-layer resist method, the two-layer resist method uses a resist having both properties of the resist and the inorganic intermediate layer in the three-layer resist method, that is, a resist having oxygen plasma resistance. In addition, the generation of cracks and pinholes is suppressed, and the process is simplified because the number of layers is reduced from three to two. However, in the three-layer resist method, a conventional resist can be used as the upper resist, whereas in the two-layer resist method, there is a problem that a new resist having oxygen plasma resistance has to be developed.

[0008] From the above background, it has excellent oxygen plasma resistance which can be used as an upper layer resist such as a two-layer resist method.
There has been a demand for the development of a high-sensitivity, high-resolution positive photoresist, in particular, an alkali developing type resist that can be used without changing the current process.

Further, in the manufacture of a super LSI, which requires processing of an ultra-fine pattern having a line width of half a micron or less, the wavelength used in an exposure apparatus used for lithography has been shortened, and now a KrF excimer laser beam is used. The use of ArF excimer laser light has been studied. In such short wavelength optical lithography, a resist generally called a chemically amplified type is used. In particular, when an ArF excimer laser beam is used, it is not appropriate to introduce a phenol structure into a binder resin, which is a main component of the resist, from the viewpoint of optical transparency of the film. In general, a resin polymer containing, as an image-forming portion, a structure capable of decomposing with an acid to generate a carboxylic acid, such as an ester, a 1-alkyladamantyl ester, or a THP-protected carboxylic acid, is used as a binder. Polysiloxane containing an image-forming portion transparent to ArF excimer laser light is disclosed in, for example, JP-A-8-16.
0623, JP-A-10-324748, JP-A-11-324
-60733 and JP-A-11-60734.

As an example of a Si-containing resist containing an image-forming portion transparent to ArF excimer laser light, maleic anhydride-unsaturated carboxylic acid t-butyl ester-
A terpolymer comprising allyltrimethylsilane is disclosed in JP-A-5-11450. This resist has excellent resolution for processing ultra-fine patterns, but has roughness (unevenness) on the edges of the resist pattern.
Was occurring. Here, the edge roughness refers to the top and bottom edges of a resist line pattern that fluctuate irregularly in a direction perpendicular to the line direction due to the characteristics of the resist. Means that the edge looks uneven. Further, there is room for improvement in the storage stability of the resist solution. For example, when a chemically amplified photoresist is stored in a liquid state, there are problems such as poor compatibility between the resin and the photoacid generator, generation of particles in the liquid, and deterioration of resist performance. Still existed.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a positive photoresist composition having improved edge roughness of a resist pattern in the manufacture of a semiconductor device. Another object of the present invention is to provide a positive photoresist composition which is excellent in low-temperature preservability, and in particular, has little change with time (increase in particles) under conditions in which the temperature is lowered, particularly at −10 ° C. is there.

[0012]

Means for Solving the Problems As a result of intensive studies on the resist composition in a positive type chemical amplification system, the present inventors have found that (A) a photoacid generator and (B) an acid-decomposable compound having a specific structural unit. Resin (C) By using a specific solvent,
It has been found that the object of the invention is achieved. That is, the above object is achieved by using a positive photoresist composition containing the following acid-decomposable resin.

(1) (A) a compound capable of generating an acid upon irradiation with actinic rays or radiation; (B) an acid-decomposable polysiloxane having at least a structural unit represented by the following general formula (I); A mixed solvent A containing at least one selected from the group consisting of at least one selected from the group of the following solvents B, or at least one selected from the group of the solvents A and at least one selected from the group of the following solvents C Group: Propylene glycol monoalkyl ether alkoxylate Group B: Propylene glycol monoalkyl ether, alkyl lactate and alkoxyalkyl propionate Group C: At least one of γ-butyrolactone, ethylene carbonate and propylene carbonate is contained. Positive photoresist composition.

[0014]

Embedded image

In the formula (I), L ¹ is -A ¹ -OCO-, -A
¹ -COO-, -A ¹ -NHCO-, -A ¹ -NHCOO
-, -A ¹ -NHCONH-, -A ¹ -CONH-, -A
¹ -OCONH- or an -A ¹ -S-. A ¹ represents an alkylene group, an arylene group, and at least one divalent linking group selected from monocyclic and bridged alicyclic structures.
M ¹ represents a single bond, an alkylene group, an arylene group, or a divalent linking group having a monocyclic or bridged alicyclic structure. R ′ to R ′ ″ each independently represent an alkyl group, a haloalkyl group, a halogen atom, an alkoxy group, a trialkylsilyl group or a trialkylsilyloxy group.

(2) (A) a compound capable of generating an acid upon irradiation with actinic rays or radiation; (B) an acid-decomposable polysiloxane having at least a structural unit represented by the following general formula (I); A mixed solvent containing at least one selected from the group consisting of at least one selected from the following solvent group B, and at least one selected from the following solvent group C: group A: propylene glycol monoalkyl ether alkoxylate group B : Propylene glycol monoalkyl ether, alkyl lactate and alkoxyalkyl propionate Group C: A positive photoresist composition containing γ-butyrolactone, ethylene carbonate and propylene carbonate.

[0017]

Embedded image

In the formula (I), L ¹ is -A ¹ -OCO-, -A
¹ -COO-, -A ¹ -NHCO-, -A ¹ -NHCOO
-, -A ¹ -NHCONH-, -A ¹ -CONH-, -A
¹ -OCONH- or an -A ¹ -S-. A ¹ represents an alkylene group, an arylene group, and at least one divalent linking group selected from monocyclic and bridged alicyclic structures.
M ¹ represents a single bond, an alkylene group, an arylene group, or a divalent linking group having a monocyclic or bridged alicyclic structure. R ′ to R ′ ″ each independently represent an alkyl group, a haloalkyl group, a halogen atom, an alkoxy group, a trialkylsilyl group or a trialkylsilyloxy group.

(3) (A) a compound capable of generating an acid upon irradiation with an actinic ray or radiation; (B) an acid-decomposable polysiloxane having at least a structural unit represented by the following general formula (I); A positive photoresist composition comprising a mixed solvent containing at least one kind and at least one of an ester solvent and an alkoxyalkyl propionate.

[0020]

Embedded image

In the formula (I), L ¹ is -A ¹ -OCO-, -A
¹ -COO-, -A ¹ -NHCO-, -A ¹ -NHCOO
-, -A ¹ -NHCONH-, -A ¹ -CONH-, -A
¹ -OCONH- or an -A ¹ -S-. A ¹ represents an alkylene group, an arylene group, and at least one divalent linking group selected from monocyclic and bridged alicyclic structures.
M ¹ represents a single bond, an alkylene group, an arylene group, or a divalent linking group having a monocyclic or bridged alicyclic structure. R ′ to R ′ ″ each independently represent an alkyl group, a haloalkyl group, a halogen atom, an alkoxy group, a trialkylsilyl group or a trialkylsilyloxy group.

(4) (A) a compound capable of generating an acid upon irradiation with actinic rays or radiation; (B) at least an acid-decomposable polysiloxane having a structural unit represented by the following general formula (I); and (C) heptanone. A positive photoresist composition comprising a solvent.

[0023]

Embedded image

In the formula (I), L ¹ is -A ¹ -OCO-, -A
¹ -COO-, -A ¹ -NHCO-, -A ¹ -NHCOO
-, -A ¹ -NHCONH-, -A ¹ -CONH-, -A
¹ -OCONH- or an -A ¹ -S-. A ¹ represents an alkylene group, an arylene group, and at least one divalent linking group selected from monocyclic and bridged alicyclic structures.
M ¹ represents a single bond, an alkylene group, an arylene group, or a divalent linking group having a monocyclic or bridged alicyclic structure. R ′ to R ′ ″ each independently represent an alkyl group, a haloalkyl group, a halogen atom, an alkoxy group, a trialkylsilyl group or a trialkylsilyloxy group.

(5) The positive electrode according to (4), wherein the solvent (C) further contains at least one of propylene glycol monoalkyl ether, alkyl lactate and alkoxyalkyl propionate. -Type photoresist composition.

(6) The solvent according to any one of the above (3) to (5), wherein the solvent (C) further contains at least one of γ-butyrolactone, ethylene carbonate and propylene carbonate. Positive photoresist composition.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. First, (B) the acid-decomposable polysiloxane (hereinafter, also referred to as an acid-decomposable resin) of the present invention will be described. In the general formula (I), L ¹ is -A ¹ -OCO
-, -A ¹ -COO-, -A ¹ -NHCO-, -A ¹ -N
^{HCOO -, - A 1 -NHCONH -} , - A 1 -CONH
-, - A ¹ -OCONH- or an -A ¹ -S-. A ¹
Represents an alkylene group, an arylene group, and at least one divalent linking group selected from monocyclic and bridged alicyclic structures. In the A ^1, an alkylene group, for example, linear or branched alkylene group having 1 to 10 carbon atoms, preferably straight-chain or branched alkylene group having 1 to 6 carbon atoms, particularly preferably Is a methylene group, an ethylene group or a propylene group. Specific examples of the arylene group include an o-phenylene group, an m-phenylene group, and a p-phenylene group. In the above A ¹ , examples of the monocyclic or bridged alicyclic structure include those shown below.

[0028]

Embedded image

[0029]

Embedded image

M ¹ represents a single bond, an alkylene group, an arylene group, or a divalent linking group having a monocyclic or bridged alicyclic structure. Here, the alkylene group has 1 to 10 carbon atoms.
Linear and branched alkylene groups. It is preferably a linear or branched alkylene group having 1 to 6 carbon atoms, particularly preferably an arylene group which is a methylene group, an ethylene group or a propylene group, or a monocyclic or bridged alicyclic structure. Examples of the divalent linking group represented by are the same as those described for A ¹ .

R ′ to R ″ ″ each independently represent an alkyl group,
And a group selected from a haloalkyl group, a halogen atom, an alkoxy group, a trialkylsilyl group, and a trialkylsilyloxy group. The alkyl group may have 1 to 1 carbon atoms.
A linear or branched alkyl group of 0 is preferable, a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable, and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, i-butyl group, s
-Butyl group and t-butyl group. Examples of the haloalkyl group include a chloromethyl group, a bromomethyl group, and an iodomethyl group. The alkoxy group may have 1 to 6 carbon atoms.
Linear or branched alkyl groups, more preferably methoxy, ethoxy, n-propyloxy, i-
Propyloxy group, n-butoxy group, i-butoxy group,
An s-butoxy group and a t-butoxy group, among which methoxy and ethoxy groups are particularly preferred.

The alkyl group of the trialkylsilyl group is a linear or branched alkyl group having 1 to 6 carbon atoms,
More preferably a methyl group, an ethyl group, an n-propyl group,
Among them, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group and a t-butyl group, among which a methyl group is most preferred. The alkyl group of the trialkylsilyloxy group is a linear or branched alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, i-butyl group, s
-Butyl group and t-butyl group, and among them, the most preferred is a methyl group.

The acid-decomposable polysiloxane preferably further contains a repeating structural unit represented by the following general formulas (II) and / or (III).

[0034]

Embedded image

In the formula (II), L ² is a single bond, -A ² -OC
^{O -, - A 2 -COO -} , - A 2 -NHCO -, - A 2 -
^{NHCOO -, - A 2 -NHCONH -} , - A 2 -CON
H -, - A ² -OCONH- or -A represents a ² -S-. A
² represents a single bond, an alkylene group or an arylene group.
M ² represents an aryl group, an aralkyl group, or a monocyclic or bridged alicyclic group.

[0036]

Embedded image

[0037] In the A ^2, alkylene groups include straight or branched alkylene group having 1 to 10 carbon atoms. It is preferably a linear or branched alkylene group having 1 to 6 carbon atoms, and particularly preferably a methylene group, an ethylene group or a propylene group. Similarly, the arylene group is o-
Specific examples include a phenylene group, an m-phenylene group, and a p-phenylene group. In the above M ^2, the aryl group, phenyl group which may have a substituent can be given as specific examples. Similarly, the aralkyl group includes a benzyl group.

Examples of the monocyclic or bridged alicyclic structure of A ² and M ² include those similar to the examples of the monocyclic or bridged alicyclic structure of M ¹ .

The general formula (III) is a siloxane structural unit derived from tetrachlorosilane, tetrahydrosilane and tetraalkoxysilane. Among them, tetramethoxysilane and tetraethoxysilane are preferable as tetrachlorosilane and tetraalkoxysilane.

The acid-decomposable polysiloxane of the present invention preferably contains 10 to 100 mol%, more preferably 30 to 70 mol%, of the unit represented by the formula (I). Further, in the acid-decomposable polysiloxane of the present invention containing the structure of the general formula (II), the structure of the formula (II) is
It is preferably contained at 0 mol%, more preferably at 40 to 60 mol%. Further, the acid-decomposable polysiloxane of the present invention containing the structure of the general formula (III) preferably contains the structure of the formula (III) in an amount of 1 to 10 mol%, more preferably 2 to 5 mol%.

The acid-decomposable polysiloxane of the present invention has the following general formula (I) for controlling solvent solubility and alkali solubility.
The structural units of (V) and / or (V) may be co-condensed.

[0042]

Embedded image

Here, W, W ¹ and W ² represent groups having neither alkali solubility nor acid decomposability. Specifically, it may have a linear group having 1 to 10 carbon atoms which may have a substituent, may have a branched group having 3 to 10 carbon atoms which may have a substituent, or may have a substituent. A cyclic alkyl group having 6 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms which may have a substituent; or an aralkyl group having 7 to 11 carbon atoms which may have a substituent. . Preferred specific examples of these groups include methyl, ethyl, n-propyl, i-propyl, n
-Butyl, i-butyl, t-butyl, n-pentyl, n
-Hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclohexyl, phenyl, naphthyl, benzyl, naphthylmethyl.
The substituents of these groups include a halogen atom,
To 6 alkoxy groups, phenoxy groups, hydroxyl groups and the like. Note that W ¹ and W ² may be the same or different.

In the acid-decomposable polysiloxane of the present invention containing the structure of the general formula (IV) and / or the general formula (V),
The content of the structure of V) and / or the structure of the formula (V) is 70 mol% or less, preferably 65 mol% or less, more preferably 60 mol% or less in all the repeating units. 7
If it exceeds 0 mol%, the resolution will deteriorate.

The acid-decomposable polysiloxane having the structural unit represented by the general formula (I) can be obtained by the following method. Trialkoxysilane or trichlorosilane linked with an alicyclic structure having an ethylenically unsaturated bond is converted to a trisubstituted silane having a corresponding R ′ to R ′ ″ in the presence of a chloroplatinic acid catalyst or a radical reaction initiator. Hydrosilylate the compound.

Thereafter, 1) a trialkoxysilane having a carboxyl group at the terminal is converted into a polysiloxane by heating in the presence of an acid and water or a base catalyst and water, and then the carboxyl group is protected with an acid-decomposable group. 2) After synthesizing a trialkoxysilane having an acid-decomposable protected carboxyl group at the terminal, a base catalyst and water are added, and the mixture is heated to form a polysiloxane. Can be synthesized.

Alternatively, an acid-decomposable group-containing polysiloxane linked to an alicyclic structure having an ethylenically unsaturated bond is reacted with the corresponding R ′ to R ′ in the presence of a chloroplatinic acid catalyst or a radical reaction initiator. There is also a method of hydrosilylating a trisubstituted silane compound having ''.

Examples of the method for introducing the acid-decomposable group include an acid-catalyzed reaction with a vinyl ether compound corresponding to the acid-decomposable group, di-t-butyl dicarbonate, trimethylsilyl chloride,
Alternatively, it can be obtained by using a known reaction such as a base catalyzed reaction with t-butyldimethylsilyl chloride.

Use of a siloxane unit having a structural unit represented by the above (IV) or (V) is preferred in view of solvent solubility, sensitivity, resolution, and rectangularity of a pattern.

Specific examples of the structural unit of the general formula (I) for the polysiloxane of the present invention are shown below, but the present invention is not limited thereto.

[0051]

Embedded image

[0052]

Embedded image

Specific examples of the structural unit of the general formula (II) for the polysiloxane of the present invention are shown below, but the present invention is not limited thereto.

[0054]

Embedded image

The weight average molecular weight of the polysiloxane of the present invention is from 500 to 10,000 as a polystyrene equivalent value measured by gel permeation chromatography.
0 is preferable, 700 to 50,000 is more preferable, and 800 to 20,000 is particularly preferable.

Next, the compound (A) which generates an acid upon irradiation with actinic rays or radiation will be described. Examples of the compound used in the present invention, which decomposes upon irradiation with actinic rays or radiation to generate an acid, include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photobleaching agent for dyes, and a photodiscoloration agent. Agents or known light used for micro resists (ultraviolet rays of 400 to 200 nm, far ultraviolet rays, particularly preferably g-rays, i-rays, KrF excimer laser light, A
A compound capable of generating an acid by rF excimer laser light, electron beam, X-ray, molecular beam or ion beam, and a mixture thereof can be appropriately selected and used.

Compounds that generate an acid upon irradiation with actinic rays or radiation used in the present invention include, for example, SI
Schlesinger, Photogr. Sci. Eng., 18, 387 (1974),
TSBal et al, Polymer, 21, 423 (1980) and the like diazonium salts, U.S. Pat.Nos. 4,069,055 and 4,069,056
No. Re27,992, ammonium salts described in JP-A-3-140140, etc., DC Necker et al, Macromolecules, 17,
2468 (1984), CS Wenet al, Teh, Proc. Conf. Rad.
Curing ASIA, p478 Tokyo, Oct (1988), U.S. Patent No. 4,06
9,055, the phosphonium salts described in 4,069,056 and the like, J.
V. Crivello et al, Macromorecules, 10 (6), 1307 (19
77), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Patent Nos. 339,049, 410,201.
Iodonium salts described in JP-A-2-150,848, JP-A-2-296,514, etc., JV Crivello etal, Polymer J. 1
7, 73 (1985), JV Crivello et al. J. Org. Chem.,
43, 3055 (1978), WR Watt et al, J. Polymer Sci.,
Polymer Chem. Ed., 22, 1789 (1984), JV Crivello
et al, Polymer Bull., 14, 279 (1985), JV Crivel
lo et al, Macromorecules, 14 (5), 1141 (1981), JV
Crivello et al, J. Polymer Sci., Polymer Chem. E
d., 17, 2877 (1979), European Patent Nos. 370,693, 161,81
No. 1, No. 410, 201, No. 339,049, No. 233,567, No. 297,
No. 443, No. 297,442, U.S. Pat.No. 3,902,114 No. 4,933,3
No. 77, No. 4,760,013, No. 4,734,444, No. 2,833,827
No. 2,904,626, 3,604,580, 3,604,
No. 581, JP-A-7-28237, sulfonium salts described in JP-A-8-27102, etc., JV Crivello et al, Macromorecules,
10 (6), 1307 (1977), JV Crivello et al, J. Polyme
r Sci., Polymer Chem. Ed., 17, 1047 (1979) and the like, CS Wen et al., Teh, Proc. Conf. R
ad. Curing ASIA, p478 Tokyo, Oct (1988), etc., onium salts such as arsonium salts, U.S. Pat.
No., JP-B-46-4605, JP-A-48-36281, JP-A-55-32
No. 070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401
No., JP-A-63-70243, organic halogen compounds described in JP-A-63-298339, etc., K. Meier et al, J. Rad.
13 (4), 26 (1986), TP Gill et al, Inorg.Chem.,
19, 3007 (1980), D. Astruc, Acc. Chem. Res., 19 (1
2), 377 (1896), and organometallic / organic halides described in JP-A-2-14145, S. Hayase et al, J. Polymer Sc
i., 25, 753 (1987), E. Reichmanis et al, J. Pholymer
Sci., Polymer Chem. Ed., 23, 1 (1985), QQ Zhu et.
al, J. Photochem., 36, 85, 39, 317 (1987), B. Amit
et al, Tetrahedron Lett., (24) 2205 (1973), DHR
Barton et al, J. Chem Soc., 3571 (1965), PM Colli
ns et al, J. Chem. Soc., PerkinI, 1695 (1975), M. Ru.
dinstein et al, Tetrahedron Lett., (17), 1445 (197
5), JW Walker et al, J. Am. Chem. Soc., 110, 7170
(1988), SC Busman et al, J. Imaging Technol., 11
(4), 191 (1985), HM Houlihan et al, Macormolecule
s, 21, 2001 (1988), PM Collins et al, J. Chem. S
oc., Chem. Commun., 532 (1972), S. Hayase et al, Mac
romolecules, 18, 1799 (1985); E. Reichman et al, J.
Electrochem. Soc., Solid State Sci. Technol., 130
(6), FM Houlihan et al, Macromolcules, 21, 2001
(1988), European Patent Nos. 0290,750, 046,083, 156,53
Nos. 5,271,851, 0,388,343, U.S. Pat.
No. 10, 4,181,531, JP-A-60-198538, JP-A-53-1
No. 33022, etc., a photoacid generator having a 0-nitrobenzyl-type protecting group, M. TUNOOKA et al, Polymer Preprints
Japan, 35 (8), G. Berneret al, J. Rad. Curing, 13
(4), WJ Mijs et al, Coating Technol., 55 (697),
45 (1983), Akzo, H. Adachi et al, Polymer Preprints,
Japan, 37 (3), European Patent Nos. 0199,672, 84,515,
044,115, 618,564, 0101,122, U.S. Pat.
Nos. 371,605 and 4,431,774, JP-A-64-18143, JP-A-Hei.
2-245756, compounds that generate sulfonic acid upon photodecomposition represented by iminosulfonate and the like described in JP-A-3-140109, JP-A-61-166544, JP-A-2-71270 and the like Disulfone compound described, JP-A-3-103854, 3-103856
And the diazoketosulfone and diazodisulfone compounds described in JP-A Nos. 4-210960 and 4-210960.

Further, a group that generates an acid by these lights,
Alternatively, a compound having a compound introduced into the main chain or side chain of a polymer, for example, ME Woodhouse et al, J. Am. Ch.
em. Soc., 104, 5586 (1982), SP Pappas et al, J. I.
maging Sci., 30 (5), 218 (1986), S. Kondo et al, Mak
romol. Chem., Rapid Commun., 9, 625 (1988), Y. Yama
da et al, Makromol.Chem., 152, 153, 163 (1972);
V. Crivello et al, J. Polymer Sci., Polymer Chem.
Ed., 17, 3845 (1979), U.S. Patent No. 3,849,137, Dokoku Patent No. 3,914,407, JP-A-63-26653, JP-A-55-164824.
No., JP-A-62-69263, JP-A-63-146038, JP-A-63-69263
Compounds described in JP-A-163452, JP-A-62-153853, JP-A-63-146029 and the like can be used.

Further, VNR Pillai, Synthesis, (1),
1 (1980), A. Abad et al, Tetrahedron Lett., (47) 45
55 (1971), DHR Barton et al, J. Chem. Soc.,
(C), 329 (1970), U.S. Patent 3,779,778, European Patent 1
Compounds that generate an acid by light described in No. 26,712 and the like can also be used.

Among the compounds capable of decomposing upon irradiation with actinic rays or radiation to generate an acid, those which are particularly effectively used are described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PA)
An S-triazine derivative represented by G2).

[0061]

Embedded image

In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group, —C (Y) ₃
Show Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image

(2) An iodonium salt represented by the following formula (PAG3) or a sulfonium salt represented by the following formula (PAG4).

[0067]

Embedded image

Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group, and a halogen atom.

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferably, it is an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or a substituted derivative thereof. Preferred substituents include an aryl group, an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group,
A carboxyl group, a hydroxy group and a halogen atom, and an alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group and an alkoxycarbonyl group.

[0070] Z ^{chromatography} represents a counter anion, for example BF ₄ ^over,
AsF ₆ ^over, PF ₆ ^over, SbF ₆ ^over, SiF ₆ ^2-, ClO ₄ ^over,
CF ₃ SO ₃ ^over perfluoroalkanesulfonic acid anion such as, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, a sulfonic acid group-containing dyes Examples include, but are not limited to:

Further, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded through a single bond or a substituent.

Specific examples include the following compounds, but are not limited thereto.

[0073]

Embedded image

[0074]

Embedded image

[0075]

Embedded image

[0076]

Embedded image

[0077]

Embedded image

[0078]

Embedded image

[0079]

Embedded image

[0080]

Embedded image

[0081]

Embedded image

[0082]

Embedded image

[0083]

Embedded image

[0084]

Embedded image

[0085]

Embedded image

The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JW Knapcz
yk et al, J. Am. Chem. Soc., 91, 145 (1969), AL
Maycok et al, J. Org.Chem., 35, 2532, (1970), E.
Goethas et al, Bull.Soc.Chem.Belg., 73, 546, (19
64), HM Leicester, J. Ame. Chem. Soc., 51, 3587.
(1929), JV Crivello et al, J. Polym. Chem. Ed.,
18, 2677 (1980); U.S. Pat.Nos. 2,807,648 and 4,24
No. 7,473, and JP-A-53-101331 can be synthesized.

(3) Disulfone derivatives represented by the following formula (PAG5) or iminosulfonate derivatives represented by the following formula (PAG6).

[0088]

Embedded image

In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group. Specific examples include the following compounds, but are not limited thereto.

[0090]

Embedded image

[0091]

Embedded image

[0092]

Embedded image

[0093]

Embedded image

[0094]

Embedded image

[0095]

Embedded image

(4) Diazosulfone Derivatives Examples of the diazodisulfone derivative compounds include those represented by the following general formula (PAG7).

[0097]

Embedded image

Here, R ²⁰⁷ and R ²⁰⁸ each independently represent an alkyl group which may have a substituent, a cycloalkyl group, or an aryl group which may have a substituent.
Here, the alkyl group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 12 carbon atoms. As the cycloalkyl group, a cyclopentyl group or a cyclohexyl group is preferable. As the aryl group, an aryl group which may have a substituent having 6 to 10 carbon atoms is preferable. Here, as the substituent, a methyl group, an ethyl group, an n-propyl group, an i-propyl group,
n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, etc. Examples thereof include an alkoxy group such as an alkyl group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, a halogen atom, a nitro group, and an acetyl group.

Specific examples of the diazodisulfone derivative compound include the following compounds. Bis (methylsulfonyl) diazomethane, bis (ethylsulfonyl) diazomethane, bis (propylsulfonyl) diazomethane,
Bis (1-methylpropylsulfonyl) diazomethane,
Bis (butylsulfonyl) diazomethane, bis (1-methylbutylsulfonyl) diazomethane, bis (heptylsulfonyl) diazomethane, bis (octylsulfonyl) diazomethane, bis (nonylsulfonyl) diazomethane, bis (decylsulfonyl) diazomethane, bis (dodecylsulfonyl) Diazomethane, bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (benzylsulfonyl) diazomethane, bis (2-chlorobenzylsulfonyl) diazomethane, bis (4-chlorobenzylsulfonyl) diazomethane, bis (phenylsulfonyl) Diazomethane, bis (4-methoxyphenylsulfonyl)
Diazomethane, bis (2-methylphenylsulfonyl)
Diazomethane, bis (3-methylphenylsulfonyl)
Diazomethane, bis (4-methylphenylsulfonyl)
Diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (2,5-dimethylphenylsulfonyl) diazomethane, bis (3,4-dimethylphenylsulfonyl) diazomethane, bis (2,4,6-
Trimethylphenylsulfonyl) diazomethane, bis (4-fluorophenylsulfonyl) diazomethane, bis (2,4-difluorophenylsulfonyl) diazomethane, bis (2,4,6-trifluorophenylsulfonyl) diazomethane, bis (4-nitrophenylsulfonyl) ) Diazomethane

Examples of the diazoketosulfone derivative compound include those represented by the following general formula (PAG8).

[0101]

Embedded image

Here, R ²⁰⁷ and R ²⁰⁸ are the same as those in (PAG7)
R ²⁰⁷ and R ²⁰⁸ have the same meanings. Specific examples of the diazoketosulfone derivative compound include the following compounds.

Methylsulfonyl-benzoyl-diazomethane, ethylsulfonyl-benzoyl-diazomethane,
Methylsulfonyl-4-bromobenzoyl-diazomethane, ethylsulfonyl-4-bromobenzoyl-diazomethane, phenylsulfonyl-benzoyl-diazomethane, phenylsulfonyl-2-methylphenyl-diazomethane, phenylsulfonyl-3-methylphenyl-diazomethane, phenylsulfonyl- 4-methylphenyl-diazomethane, phenylsulfonyl-3-methoxyphenyl-diazomethane, phenylsulfonyl-4-methoxyphenyl-diazomethane, phenylsulfonyl-3
-Chlorobenzoyl-diazomethane, phenylsulfonyl-4-chlorophenyl-diazomethane, tolylsulfonyl-3-chlorobenzoyl-diazomethane, tolylsulfonyl-4-chlorophenyl-diazomethane, phenylsulfonyl-4-fluorophenyl-diazomethane,
Tolylsulfonyl-4-fluorophenyl-diazomethane

The amount of the photoacid generator (A) used is usually in the range of 0.001 to 40% by weight based on the total weight (excluding the coating solvent) of the positive photoresist composition of the present invention. It is preferably used in the range of 0.01 to 20% by weight, more preferably 0.1 to 5% by weight. If the amount of the compound that decomposes upon irradiation with actinic rays or radiation to generate an acid is less than 0.001% by weight, the sensitivity becomes low. If the amount is more than 40% by weight, the light absorption of the resist becomes high. This is not preferable because the profile is deteriorated and the process (especially baking) margin is narrowed.

The positive photoresist composition of the present invention comprises
(C) It contains a solvent. As the component (C), at least one of propylene glycol monoalkyl ether carboxylate (also referred to as a group A solvent) and at least one of propylene glycol monoalkyl ether, alkyl lactate and alkoxyalkyl propionate (B And / or γ-butyrolactone, ethylene carbonate and propylene carbonate (also referred to as a group C solvent). That is, as the component (C), a combination of a solvent of Group A and a solvent of Group B, a combination of a solvent of Group A and a solvent of Group C, a solvent of Group A, a solvent of Group B and a solvent of Group C Is used. When a combination of the solvent of Group A and the solvent of Group B is used, the edge roughness is particularly excellent. The combination of the solvent of Group A and the solvent of Group C is particularly excellent in the stability over time of the resist solution. When a combination of the group A solvent, the group B solvent and the group C solvent is used, both the edge roughness and the stability over time of the resist solution are particularly improved. Preferred examples of the propylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, and propylene glycol monoethyl ether propionate.

As propylene glycol monoalkyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether can be preferably exemplified. Preferred examples of the alkyl lactate include methyl lactate and ethyl lactate. Preferred examples of the alkoxyalkyl propionate include 3-ethoxyethyl propionate, 3-methoxymethyl propionate, 3-methoxyethyl propionate, and 3-ethoxymethyl propionate.

The weight ratio (A: B) of the solvent of Group A to the solvent of Group B is preferably 90:10 to 15:85.
The ratio is more preferably 85:15 to 20:80, and still more preferably 80:20 to 25:75. The weight ratio (A: C) of the solvent of Group A to the solvent of Group C is 99.
9: 0.1 to 75:25 is preferable, and 9 is more preferable.
9: 1 to 80:20, more preferably 97: 3 to
85:15.

When these three solvents are combined,
The use weight ratio of the solvent of the group C is 0.1 to the total solvent.
It is preferably 25% by weight, more preferably 1 to 20% by weight, and still more preferably 3 to 17% by weight. In the present invention, the solid content of the resist composition containing each of the above components is preferably dissolved in the mixed solvent at a solid concentration of 3 to 25% by weight, more preferably 5 to 22% by weight, and still more preferably 5 to 22% by weight. It is 7 to 20% by weight.

Preferred combinations of the mixed solvent containing propylene glycol monoalkyl ether carboxylate in the present invention include propylene glycol monomethyl ether acetate +
Propylene glycol monomethyl ether Propylene glycol monomethyl ether acetate +
Ethyl lactate Propylene glycol monomethyl ether acetate +
3-ethoxyethyl propionate propylene glycol monomethyl ether acetate +
γ-butyrolactone propylene glycol monomethyl ether acetate +
Ethylene carbonate Propylene glycol monomethyl ether acetate +
Propylene carbonate Propylene glycol monomethyl ether acetate +
Propylene glycol monomethyl ether + γ-butyrolactone Propylene glycol monomethyl ether acetate +
Ethyl lactate + γ-butyrolactone propylene glycol monomethyl ether acetate +
3-ethoxyethyl propionate + γ-butyrolactone propylene glycol monomethyl ether acetate +
Propylene glycol monomethyl ether + ethylene carbonate Propylene glycol monomethyl ether acetate +
Ethyl lactate + ethylene carbonate propylene glycol monomethyl ether acetate +
3-ethoxyethyl propionate + ethylene carbonate propylene glycol monomethyl ether acetate +
Propylene glycol monomethyl ether + propylene carbonate Propylene glycol monomethyl ether acetate +
Ethyl lactate + propylene carbonate propylene glycol monomethyl ether acetate +
3-ethoxyethyl propionate + propylene carbonate.

A particularly preferred solvent combination is propylene glycol monomethyl ether acetate +
Propylene glycol monomethyl ether + γ-butyrolactone Propylene glycol monomethyl ether acetate +
Ethyl lactate + γ-butyrolactone propylene glycol monomethyl ether acetate +
3-ethoxyethyl propionate + γ-butyrolactone propylene glycol monomethyl ether acetate +
Propylene glycol monomethyl ether + ethylene carbonate Propylene glycol monomethyl ether acetate +
Ethyl lactate + ethylene carbonate propylene glycol monomethyl ether acetate +
3-ethoxyethyl propionate + ethylene carbonate propylene glycol monomethyl ether acetate +
Propylene glycol monomethyl ether + propylene carbonate Propylene glycol monomethyl ether acetate +
Ethyl lactate + propylene carbonate propylene glycol monomethyl ether acetate +
3-ethoxyethyl propionate + propylene carbonate.

The component (C) of the present invention includes at least one kind of alkyl lactate (also referred to as the solvent of (1)) and at least one kind of ester solvent and alkoxyalkyl propionate ((2) Solvent)
And a mixed solvent containing When a combination of the solvent (1) and the solvent (2) is used, the edge roughness is particularly excellent. Preferred examples of the alkyl lactate include methyl lactate and ethyl lactate.

Preferred examples of the ester solvent include butyl acetate, pentyl acetate, hexyl acetate, and butyl propionate, and more preferably butyl acetate.
Preferred examples of the alkoxyalkyl propionate include 3-ethoxyethyl propionate, 3-methoxymethyl propionate, 3-methoxyethyl propionate, and 3-ethoxymethyl propionate.

The weight ratio of the solvent (1) to the solvent (2) ((1) :( 2)) is 90:10 to 15:85.
And more preferably 85:15 to 20:80, and still more preferably 80:20 to 25:75.

In the present invention, the mixed solvent of (C)
Further, it is preferable to contain at least one of γ-butyrolactone, ethylene carbonate and propylene carbonate (also referred to as a solvent of (3)). By adding the solvent of (3), generation of particles in the resist composition solution can be suppressed, and further generation of particles in the solution over time can be suppressed. The use weight ratio of the solvent (3) is preferably 0.1 to 25% by weight, more preferably 1 to 20% by weight, and more preferably 3 to 15% with respect to the total solvent. In the present invention, the solid content of the resist composition containing each of the above components is preferably dissolved in the mixed solvent at a solid concentration of 3 to 25% by weight, more preferably 5 to 22% by weight, and still more preferably 5 to 22% by weight. 7
-20% by weight.

Preferred combinations of the mixed solvent containing alkyl lactate in the present invention include ethyl lactate + butyl acetate, ethyl lactate + butyl acetate + γ-butyrolactone, ethyl lactate + butyl acetate + ethylene carbonate,
Ethyl lactate + butyl acetate + propylene carbonate, ethyl lactate + 3-ethoxyethyl propionate + γ-butyrolactone, ethyl lactate + 3-ethoxyethyl propionate + ethylene carbonate, ethyl lactate + 3-ethoxyethyl propionate + propylene carbonate. , More preferably ethyl lactate + butyl acetate +
γ-butyrolactone, ethyl lactate + butyl acetate + ethylene carbonate, ethyl lactate + butyl acetate + propylene carbonate, ethyl lactate + 3-ethoxyethyl propionate + γ-butyrolactone, ethyl lactate + 3-ethoxyethyl propionate + ethylene carbonate, ethyl lactate + 3-ethoxyethyl propionate + propylene carbonate.

The component (C) of the present invention is a solvent containing heptanone (also referred to as a solvent of (4)). Examples of heptanone include 2-heptanone, 3-heptanone, and 4-heptanone, and preferably 2-heptanone. By using a heptanone-based solvent, the edge roughness of the resist pattern is improved. Further, as the component (C), at least one of propylene glycol monoalkyl ether, alkyl lactate and alkoxyalkyl propionate ((5)
Is also referred to as a solvent). Thereby, the edge roughness of the resist pattern is further improved.

Preferred examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether and propylene glycol monoethyl ether. Preferred examples of the alkyl lactate include methyl lactate and ethyl lactate. Preferred examples of the alkoxyalkyl propionate include 3-ethoxyethyl propionate, 3-methoxymethyl propionate, 3-methoxyethyl propionate, and 3-ethoxymethyl propionate.

The amount of the solvent (4) used is usually at least 30% by weight, preferably at least 40% by weight, based on the total solvent.
The content is more preferably 50% by weight or more. The amount of the solvent (5) to be used is generally 5 to 70% by weight, preferably 10 to 60% by weight, more preferably 1 to 60% by weight, based on the total solvent.
5 to 50% by weight. If the amount of the solvent (5) is less than the above range, the effect of adding the solvent is reduced, and if it exceeds 70% by weight, problems such as deterioration of coating properties may occur, which is not preferable.

In the present invention, the solvent (C) preferably further contains at least one of γ-butyrolactone, ethylene carbonate and propylene carbonate (also referred to as the solvent (6)). By adding the solvent of (6), generation of particles in the resist composition solution can be suppressed, and further generation of particles in the solution over time can be suppressed. The use weight ratio of the solvent (6) is preferably from 0.1 to 25% by weight, more preferably from 1 to 20% by weight, more preferably from 3 to 15%, based on the total solvent. In the present invention, the solid content of the resist composition containing each of the above components is preferably dissolved in the mixed solvent at a solid concentration of 3 to 25% by weight, more preferably 5 to 22% by weight, and still more preferably 5 to 22% by weight. 7-2
0% by weight.

The preferred combination of the mixed solvent containing heptanone in the present invention is 2-heptanone +
Propylene glycol monomethyl ether, 2-heptanone + ethyl lactate, 2-heptanone + 3-ethoxyethyl propionate, 2-heptanone + γ-butyrolactone, 2-heptanone + ethylene carbonate, 2-heptanone + propylene carbonate, 2-heptanone + propylene glycol Monomethyl ether + γ-butyrolactone, 2-heptanone + ethyl lactate + γ-butyrolactone, 2-heptanone + 3-ethoxyethyl propionate + γ-butyrolactone, 2-heptanone + propylene glycol monomethyl ether + ethylene carbonate, 2-heptanone + ethyl lactate + ethylene Carbonate, 2-heptanone + 3-ethoxyethyl propionate + ethylene carbonate, 2-heptanone + propylene glycol monomer Ether + propylene carbonate, 2-heptanone + ethyl lactate + propylene carbonate, 2-heptanone + 3-ethoxyethyl propionate + propylene carbonate. More preferably, 2-heptanone + propylene glycol monomethyl ether + γ-butyrolactone, 2-heptanone + ethyl lactate + γ-butyrolactone, 2-heptanone + 3-
Ethoxyethyl propionate + γ-butyrolactone,
2-heptanone + propylene glycol monomethyl ether + ethylene carbonate, 2-heptanone + ethyl lactate + ethylene carbonate, 2-heptanone + 3-ethoxyethyl propionate + ethylene carbonate,
2-heptanone + propylene glycol monomethyl ether + propylene carbonate, 2-heptanone + ethyl lactate + propylene carbonate, 2-heptanone + 3
-Ethoxyethyl propionate + propylene carbonate.

The positive photoresist composition of the present invention may contain an organic basic compound. This is preferable because the storage stability is improved and the line width change due to PED is reduced. Preferred organic basic compounds that can be used in the present invention are compounds that are more basic than phenol. Among them, a nitrogen-containing basic compound is preferable. Preferred chemical environments include the following formulas (A) to (A).
(E) Structure can be mentioned.

[0122]

Embedded image

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are the same or different and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl having 1 to 6 carbon atoms. Group or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ²⁵¹ and R ²⁵² may be bonded to each other to form a ring.

[0124]

Embedded image

In the above formula (E), R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ are the same or different and represent an alkyl group having 1 to 6 carbon atoms.

Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferred is a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom. Or a compound having an alkylamino group. Preferred specific examples are substituted or unsubstituted guanidine,
Substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, substituted or 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, substituted or unsubstituted aminoalkylmorpholine, etc. Is mentioned. Preferred substituents are an amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group It is.

Particularly preferred compounds are 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-methylpyridine, 3-aminoethylpyridine, 4-
Aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2
-Aminoethyl) piperidine, 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) morpholin, diazabicycloundecene (DBU), diazabicyclononene (DB
N), diazabicyclooctane and the like, but are not limited thereto.

These nitrogen-containing basic compounds are used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is the photosensitive resin composition (excluding the solvent) 1
The amount is usually 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 00 parts by weight. If the amount is less than 0.001 part by weight, the above effects cannot be obtained. On the other hand, if it exceeds 10 parts by weight, the sensitivity tends to decrease and the developability of the unexposed part tends to deteriorate.

The positive photoresist composition of the present invention comprises
It is preferable to contain at least one surfactant of a fluorine-based surfactant, a silicon-based surfactant, a surfactant containing both a fluorine atom and a silicon atom, and a nonionic surfactant. Among them, a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom are particularly preferable.

As these surfactants, for example, those described in
No. 62-36663, JP-A-61-226746, JP-A-61-226745,
JP-A-62-170950, JP-A-63-34540, JP-A-7-23016
No. 5, JP-A-8-62834, JP-A-9-54432, JP-A-9-598
The surfactant described in No. 8 can be used, and the following commercially available surfactant can be used as it is. Commercially available surfactants that can be used, for example, F-top EF301, EF3
03, (Shin-Akita Chemical Co., Ltd.), Florado FC430, 431 (Sumitomo 3M), MegaFac F171, F173, F176, F
189, R08 (Dainippon Ink Co., Ltd.), Surflon S-38
2, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.)
), Troysol S-366 (Troy Chemical Co., Ltd.)
) Or a silicon-based surfactant. In addition, polysiloxane polymer KP
-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

Specific examples of other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; Ethylene octyl phenol ether, polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonyl phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, Sorbitan trioleate, sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; Can be mentioned. The amount of the surfactant is usually 0.001% by weight to 2% by weight, preferably 0.1% by weight, based on the solid content in the composition of the present invention.
It is from 01% by weight to 1% by weight. These surfactants may be added alone or in some combination.

The positive photoresist composition of the present invention may further contain an acid-decomposable dissolution inhibiting compound, a dye,
A plasticizer, a surfactant other than the above, a photosensitizer, a compound that promotes solubility in a developer, and the like can be contained.

The positive photoresist composition of the present invention is applied onto a substrate (eg, a silicon / silicon dioxide coating) such as used in the production of precision integrated circuit devices by an appropriate application method such as a spinner or a coater. By exposing through a predetermined mask, baking and developing, a good resist pattern can be obtained.

The developer for the positive photoresist composition of the present invention includes, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium phosphate, sodium metasilicate, and aqueous ammonia. , Ethylamine, primary amines such as n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, and alcoholamines such as dimethylethanolamine and triethanolamine. , Amides such as formamide and acetamide, tetramethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, tetraethylammonium hydroxide, tributylmethylammonium hydroxide, Ethanol ammonium hydroxide, methyl triethanol ammonium hydroxide,
Quaternary ammonium salts such as benzylmethyldiethanolammonium hydroxide, benzyldimethylethanolammonium hydroxide, benzyltriethanolammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide; cyclic amines such as pyrrole and piperidine; There are aqueous solutions of alkalis.

When the resist of the positive photoresist composition of the present invention is used as the upper resist of a two-layer resist, the lower organic polymer film is etched by oxygen plasma using the upper resist pattern as a protective mask. The upper resist has sufficient resistance to oxygen plasma. Although the oxygen plasma resistance of the positive photoresist composition of the present invention depends on the silicon content of the upper resist, the etching apparatus, and the etching conditions, the etching selectivity (the etching rate ratio between the lower resist and the upper resist) is 10%. It can be taken as a sufficiently large value of ~ 100.

In the pattern forming method using the positive photoresist composition of the present invention, first, an organic polymer film is formed on a substrate to be processed. The organic polymer film may be various known photoresists, and examples thereof include FH series and FHi series manufactured by Fujifilm Olin Co., or OiR series manufactured by Olin Co., and PFI series manufactured by Sumitomo Chemical Co., Ltd. The formation of the organic polymer film is performed by dissolving these in an appropriate solvent and applying the resulting solution by a spin coating method, a spraying method or the like. Next, a film of the positive photoresist composition of the present invention is formed on the first layer of the organic polymer film. This is performed by dissolving the resist material in an appropriate solvent in the same manner as in the first layer, and applying the resulting solution by spin coating, spraying, or the like. The obtained two-layer resist is then subjected to a pattern forming step. As a first step, a pattern forming process is first performed on the second layer, that is, the film of the upper photoresist composition. Perform mask alignment as necessary, and irradiate high-energy radiation through this mask to make the irradiated portion of the photoresist composition soluble in an alkaline aqueous solution,
The pattern is formed by developing with an alkaline aqueous solution.

Next, as a second step, the organic polymer film is etched. This operation is performed by oxygen plasma etching using the film pattern of the resist composition as a mask to form a fine pattern having a high aspect ratio. I do. The etching of the organic polymer film by the oxygen plasma etching is exactly the same technique as the plasma ashing used when the resist film is peeled off after the etching of the substrate is completed by the conventional photoetching operation. This operation can be performed by, for example, a cylindrical plasma etching apparatus or a parallel flat slope plasma etching apparatus using oxygen as a reactive gas, that is, an etching gas. Further, the substrate is processed using this resist pattern as a mask. As a processing method, a dry etching method such as sputter etching, gas plasma etching, or ion beam etching can be used.

The etching treatment by the two-layer film resist method including the resist film of the present invention is completed by the operation of removing the resist film. The removal of the resist layer can be carried out simply by dissolving the organic polymer material of the first layer. Since this organic polymer material is an arbitrary photoresist and has not been altered (hardened or the like) at all in the photoetching operation, an organic solvent of each known photoresist itself can be used. Or,
By a process such as plasma etching, separation can be performed without using a solvent.

[0139]

EXAMPLES Hereinafter, the present invention will be described with reference to the following synthetic examples, examples, and comparative examples. However, the present invention is not limited to the following examples.

Synthesis Example 1 (Synthesis of Resin (1)) (2-hydroxyethyl) tris (trimethylsilyl)
58.4 g of silane and 30.8 g of cyclohexanedicarboxylic anhydride were dissolved in 500 ml of THF.
-Dimethylaminopyridine (2 g) was added and reacted at 60 ° C under nitrogen for 6 hours. 34.0 g of chloromethyltrimethoxysilane was added thereto, and 19.0 g of diazabicycloundecene was added thereto. After filtering off the white precipitate, THF was distilled off to obtain a trimethoxysilane intermediate.

To 46.5 g of the above intermediate, 31.2 g of cyclohexyltrimethoxysilane was added to 200 ml of N, N-dimethylacetamide.
After adding 5 g of -dimethylaminopyridine, the mixture was reacted at 60 ° C for 3 hours and further at 140 ° C for 3 hours. After the reaction solution was returned to room temperature, it was poured into 3 L of distilled water with stirring to obtain a white powdery polymer. 200 ml of this in acetone
And the oligomer component of the polymer is separated and removed by adding distilled water with stirring, and the lower layer is distilled water 2
The precipitate was reprecipitated in L to obtain a white polymer. When the average molecular weight of this polymer was measured by GPC (polystyrene standard), the weight average molecular weight was 3900, and the content of components having a molecular weight of 1,000 or less was 3% by GPC area ratio.

In the same manner, the following polysiloxane was synthesized.

[0143]

Embedded image

Examples 1 to 44 and Comparative Examples 1 to 7 (Preparation and Evaluation of Positive Resist Composition) 2 g of each of the resins shown in Tables 1 to 4 synthesized in the above Synthesis Examples and the photoacids shown in Tables 1 to 4 were used. Generator 150mg, Organic basic compound 30m
g, and 10 mg of a surfactant.
After dissolving in a solvent shown in Tables 1 to 4 at a ratio of 0.
The mixture was filtered through a 1 μm microfilter to prepare positive resist compositions of Examples 1 to 44. Comparative Examples 1 to 7
A positive resist composition was prepared in the same manner as in Examples 1 to 44, except that the above resin and photoacid generator were used.

As the solvent, S1: propylene glycol monomethyl ether acetate S2: propylene glycol monomethyl ether propionate S3: ethyl lactate S4: butyl acetate S5: 2-heptanone S6: propylene glycol monomethyl ether S7: ethoxyethyl propionate S8 : Γ-butyrolactone S9: ethylene carbonate S10: propylene carbonate S11: cyclohexanone

As the surfactant, W-1: Megafac F176 (Dainippon Ink Co., Ltd.)
(Fluorine) W-2: Megafac R08 (Dai Nippon Ink Co., Ltd.)
(Fluorine and silicone type) W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) W-4: Polyoxyethylene nonylphenyl ether W-5: Troysol S-366 (Troy Chemical Co., Ltd.)
Made)

Examples of the organic basic compound include: 1: DBU (1,8-diazabicyclo [5.4.0]-
7-undecene) 2: 4-DMAP (4-dimethylaminopyridine) 3: TPI (2,4,5-triphenylimidazole)

[0148]

[Table 1]

[0149]

[Table 2]

[0150]

[Table 3]

[0151]

[Table 4]

(Evaluation test) FHi-
A 028D resist (a resist for i-line, manufactured by Fujifilm Ohlin Co., Ltd.) is applied using a coater CDS-650 manufactured by Canon, and baked at 90 ° C. for 90 seconds to form a film having a thickness of 0.83 μm.
Was obtained. When this was further heated at 200 ° C. for 3 minutes, the film thickness became 0.71 μm. The above-prepared resist solution was applied thereon, baked at 140 ° C. for 90 seconds, and applied to a thickness of 0.20 μm.

The wafer thus obtained was exposed to an ArF excimer laser stepper while changing the exposure amount and the focus by mounting a resolving power mask. Then, after heating at 110 ° C. for 90 seconds in a clean room, the solution was heated to 60% with a tetramethylammonium hydroxide developer (2.38%).
After developing for 2 seconds, rinsing with distilled water and drying were performed to obtain a pattern. The resist pattern of the silicon wafer thus obtained was observed with a scanning electron microscope, and the resist was evaluated as follows. Tables 5 to 8 show these evaluation results.

[Edge Roughness]: The edge roughness was measured using a length-measuring scanning electron microscope (SEM).
14 μm repeating pattern (line and space =
1 / 1.2) Perform with the edge roughness of the pattern, detect line pattern edges at a plurality of positions in the measurement monitor, and use the variance (3σ) of variation in the detected positions as an index of the edge roughness. preferable.

[Number of Particles and Increase in Number of Particles after Preservation with Time]: The positive photoresist composition solution (coating solution) prepared as described above was prepared immediately after preparation (particle initial value) and at -10 ° C. After standing for a week (the number of particles after aging), the number of particles in the liquid was counted using a particle counter manufactured by Rion. Along with the initial particle value, (number of particles after aging)
-The particle increase calculated by (initial value of particles) was evaluated.

[0156]

[Table 5]

[0157]

[Table 6]

[0158]

[Table 7]

[0159]

[Table 8]

As shown in Tables 5 to 8, the positive photoresist compositions of the present invention exhibited excellent performance in all evaluation items.

[0161]

According to the present invention, a positive photoresist composition having improved edge roughness of a resist pattern in the manufacture of a semiconductor device can be provided. Further, it is possible to provide a positive photoresist composition which is excellent in low-temperature preservability and, specifically, has little change with time (increase in particles) under the condition where the temperature is lowered, such as −10 ° C.

Claims (6)

[Claims] (1) a compound capable of generating an acid upon irradiation with actinic rays or radiation; (B) an acid-decomposable polysiloxane having at least a structural unit represented by the following general formula (I); A mixed solvent group A containing at least one selected from the following solvent B group and at least one selected from the solvent group A and at least one selected from the following solvent group C : Propylene glycol monoalkyl ether alkoxylate Group B: propylene glycol monoalkyl ether, alkyl lactate and alkoxyalkyl propionate Group C: characterized by containing at least one of γ-butyrolactone, ethylene carbonate and propylene carbonate. Positive photoresist composition. Embedded image In the formula (I), L ¹ represents —A ¹ —OCO—, —A ¹ —COO
-, -A ¹ -NHCO-, -A ¹ -NHCOO-, -A ^{1
-NHCONH -, - A 1 -CONH -} , - A 1 -OCO
NH- or an -A ¹ -S-. A ¹ represents an alkylene group, an arylene group, and at least one divalent linking group selected from monocyclic and bridged alicyclic structures. M ¹ represents a single bond, an alkylene group, an arylene group, or a divalent linking group having a monocyclic or bridged alicyclic structure. R '~
R ′ ″ independently represents an alkyl group, a haloalkyl group, a halogen atom, an alkoxy group, a trialkylsilyl group or a trialkylsilyloxy group. 2. Compound (A) which generates an acid upon irradiation with actinic rays or radiation (B) At least the following general formula (I)
(C) at least one member selected from the following solvent group A, at least one member selected from the following solvent group B, and at least one member selected from the following solvent group C: Group A: propylene glycol monoalkyl ether alkoxylate Group B: propylene glycol monoalkyl ether, alkyl lactate and alkoxyalkyl propionate Group C: containing γ-butyrolactone, ethylene carbonate and propylene carbonate A positive photoresist composition comprising: Embedded image In the formula (I), L ¹ represents —A ¹ —OCO—, —A ¹ —COO
-, -A ¹ -NHCO-, -A ¹ -NHCOO-, -A ^{1
-NHCONH -, - A 1 -CONH -} , - A 1 -OCO
NH- or an -A ¹ -S-. A ¹ represents an alkylene group, an arylene group, and at least one divalent linking group selected from monocyclic and bridged alicyclic structures. M ¹ represents a single bond, an alkylene group, an arylene group, or a divalent linking group having a monocyclic or bridged alicyclic structure. R '~
R ′ ″ independently represents an alkyl group, a haloalkyl group, a halogen atom, an alkoxy group, a trialkylsilyl group or a trialkylsilyloxy group. (A) a compound capable of generating an acid upon irradiation with actinic rays or radiation; (B) at least an acid-decomposable polysiloxane having a structural unit represented by the following general formula (I); and (C) an alkyl lactate. A positive photoresist composition comprising a mixed solvent containing at least one of an ester solvent and at least one of an alkoxyalkylpropionate. Embedded image In the formula (I), L ¹ represents —A ¹ —OCO—, —A ¹ —COO
-, -A ¹ -NHCO-, -A ¹ -NHCOO-, -A ^{1
-NHCONH -, - A 1 -CONH -} , - A 1 -OCO
NH- or an -A ¹ -S-. A ¹ represents an alkylene group, an arylene group, and at least one divalent linking group selected from monocyclic and bridged alicyclic structures. M ¹ represents a single bond, an alkylene group, an arylene group, or a divalent linking group having a monocyclic or bridged alicyclic structure. R '~
R ′ ″ independently represents an alkyl group, a haloalkyl group, a halogen atom, an alkoxy group, a trialkylsilyl group or a trialkylsilyloxy group. 4. A compound comprising (A) a compound capable of generating an acid upon irradiation with actinic rays or radiation; (B) an acid-decomposable polysiloxane having at least a structural unit represented by the following general formula (I); and (C) a solvent containing heptanone. A positive photoresist composition comprising: Embedded image In the formula (I), L ¹ represents —A ¹ —OCO—, —A ¹ —COO
-, -A ¹ -NHCO-, -A ¹ -NHCOO-, -A ^{1
-NHCONH -, - A 1 -CONH -} , - A 1 -OCO
NH- or an -A ¹ -S-. A ¹ represents an alkylene group, an arylene group, and at least one divalent linking group selected from monocyclic and bridged alicyclic structures. M ¹ represents a single bond, an alkylene group, an arylene group, or a divalent linking group having a monocyclic or bridged alicyclic structure. R '~
R ′ ″ independently represents an alkyl group, a haloalkyl group, a halogen atom, an alkoxy group, a trialkylsilyl group or a trialkylsilyloxy group. 5. The positive-type photo according to claim 4, wherein the solvent (C) further contains at least one of propylene glycol monoalkyl ether, alkyl lactate and alkoxyalkyl propionate. Resist composition. 6. The positive photoresist according to claim 3, wherein the solvent (C) further contains at least one of γ-butyrolactone, ethylene carbonate and propylene carbonate. Composition.