JP2000281642A - New 1,4-phenylenedisulfonamide derivative and 1,4- phenylenedisulfonyloxyimide compound having acid generating ability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound capable of generating an acid by exposure to radiations such as far ultraviolet rays, especially a KrF eximer laser, utilizable as a photoacid generator, having an acid generating ability and useful as a photoresist for producing an LSI in the electronics field. SOLUTION: This compound is represented by formula I [R1 is H, a 1-4C alkyl or SO2R2 (R2 is a 1-12C alkyl or the like)], e.g. 5-(2-methylcyclopentane-1,3- dione)2-methyl-1,4-phenylenedimethanesulfonamide. Furthermore, the above compound (when R1 is H atom) is obtained by reacting a compound represented by formula II with R2SO2Cl/alkali, reacting the resultant compound with Pb(CH3 CO2)4/CH3CH2OH, deactivating the Pb(CH3CO2)4 with ethylene glycol and reacting the prepared compound with a compound represented by formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel compound useful as a radiation-sensitive material sensitive to far ultraviolet light, an electron beam, X-rays, etc., and more particularly to a KrF excimer laser beam (248.4 nm), ArF The present invention relates to a novel compound which generates an acid by irradiating radiation such as excimer laser light (193 nm), an electron beam, and X-ray. The compounds of the present invention can be used in LSIs and VLs in the electronics field.
It is used as a photoresist for manufacturing SI.

[0002]

2. Description of the Related Art In the field of microfabrication represented by the manufacture of integrated circuit elements, in order to obtain a higher degree of integration, the development of lithography technology that enables submicrometer (0.20 μm) level microfabrication. The use of radiation having a shorter wavelength is being studied as one of the means. Examples of such short-wavelength radiation include a bright line spectrum of a mercury lamp, deep ultraviolet rays represented by an excimer laser, X-rays, and electron beams. Particularly, a KrF excimer laser or Ar
F excimer lasers are receiving attention. As one method for obtaining high-sensitivity, high-resolution resists using these radiations, so-called chemically amplified resists have been proposed. For example, a positive chemically amplified resist is composed of a radiation-sensitive acid generator (hereinafter, referred to as a “photoacid generator”) that generates an acid upon irradiation with a component that is insoluble in a developing solution and is acid dissociated. And a component which has a hydrophilic functional group and which becomes easily soluble in a developer when the functional group is eliminated using an acid as a catalyst.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel 1,4-phenylenedisulfonamide derivative and 1,4-phenylenedisulfoamide having an acid-generating ability, which can be used as a photoacid generator. An object of the present invention is to provide a nitroximide compound.

[0004]

Means for Solving the Problems [A] Regarding 1,4-phenylenedisulfonamide derivative [A-1] Structure The 1,4-phenylenedisulfonamide derivative of the present invention is represented by the following formula (1).

[0005]

Embedded image[Wherein, R¹Is a hydrogen atom, a C 1-4 linear or
Branched alkyl group or -SO_TwoR^TwoOrganic group represented by
And R^TwoRepresents a linear, branched or C1-C12
Is a cyclic alkyl group, a group represented by the following formula (1a),
Or p-R^s1-C ₆H_Four-(However, R^{s 1}Is 1 to 4 carbon atoms
Is a linear or branched alkyl group. ) Indicates a group
You.

Embedded image ]

One molecule of the compound represented by the above formula (1) has two R ^{1 s,} which may be the same or different. When R ¹ is a linear or branched alkyl group, specific examples thereof include a methyl group, an ethyl group,
n-propyl group, n-butyl group, i-propyl group, se
Examples thereof include a c-butyl group and a tert-butyl group.
In the present invention, R ¹ is a hydrogen atom or -S
It is preferably an organic group represented by O ₂ R ² . The group —SO ₂ R ² in the above formula (1) is a functional group which is eliminated by irradiation with radiation to generate a sulfonic acid R ² SO ₃ H. One molecule of the compound represented by the above formula (1) has two to four R ²
Which may be the same or different groups. When R ² is a linear, branched or cyclic alkyl group, specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group,
Examples include a sec-butyl group, a tert-butyl group, a cyclohexyl group, and the like. In the present invention, all of R ² are methyl groups, or both of the above formula (1a)
The groups shown in the above are preferred. Also, R ² is p-R ^s1
When it is a —C ₆ H ₄ — group, specific examples of R ^s1 include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an i-type group.
-Propyl group, sec-butyl group, tert-butyl group and the like. In the present invention, R ^s1 is preferably a methyl group or a tert-butyl group.

[A-2] Representative Synthetic Method [0007] When R ¹ is a hydrogen atom, the 1,4-phenylenedisulfonamide derivative of the present invention can be synthesized by, for example, a method represented by the following formula (a). .

[0008]

(Equation 1)

Alternatively, a method represented by the following formula (a ') may be used.

[0010]

(Equation 2)

[0011] Incidentally, when R ¹ is an organic group represented by -SO ₂ R ² is, R ¹ is hydrogen atom in 1,4-phenylene sulfonamide derivatives, pyridine presence, R ² S
It can be synthesized by a method such as reacting a sulfonyl chloride represented by O ₂ Cl.

[A-3] Photodecomposition Mechanism The 1,4-phenylenedisulfonamide derivative of the present invention generates an acid by irradiation with radiation such as an ArF excimer laser or a KrF excimer laser, for example, according to the following formula (a ″). I do.

[0013]

(Equation 3)

[B] 1,4-phenylenedisulfonyloxyimide compound [B-1] Structure The 1,4-phenylenedisulfonyloxyimide compound of the present invention is represented by the following formula (2).

[0015]

Embedded image Wherein, R ³ represents a linear 1 to 12 carbon atoms, branched or cyclic alkyl group, a group represented by the following formula (2a) or _{^{p-R s2 -C 6 H 4}} , - ( provided that R ^s2 has 1 to 4 carbon atoms
Is a linear or branched alkyl group. ) Represents a group.

Embedded image ]

The group SO in the above formula (2)_TwoR^ThreeIs the radiation
By irradiation with X-rays to release sulfonic acid R^ThreeSO_ThreeProduces H
It is a functional group. One molecule of the compound represented by the above formula (2) is two
R ^ThreeThese are the same groups but different groups.
It may be. This R^ThreeIs linear, branched or cyclic
When the alkyl group is, a specific example thereof is methyl
Group, ethyl group, n-propyl group, n-butyl group, i-
Propyl group, sec-butyl group, tert-butyl group,
And a clohexyl group. In the present invention,
R^ThreeAre both methyl groups, or both are
It is preferably a group represented by the formula (2a). Also, R^Three
Is p-R^s2-C₆H_Four-R^s2Examples of
Are methyl, ethyl, n-propyl, n-butyl
Tyl group, i-propyl group, sec-butyl group, tert
-Butyl group and the like. In the present invention, R^s2
Is preferably a methyl group or a tert-butyl group.
New

[B-2] Representative Synthesis Method The 1,4-phenylenedisulfonyloxyimide compound of the present invention can be synthesized, for example, by the method shown in the following formula (b).

[0018]

(Equation 4)

[B-3] Photodecomposition mechanism The 1,4-phenylenedisulfonyloxyimide compound of the present invention can be converted into an acid according to the following formula (b ″) by irradiation with radiation such as an ArF excimer laser or a KrF excimer laser. Occurs.

[0020]

(Equation 5)

[C] Applications 1,4-phenylenedisulfonamide derivatives of the present invention,
The 1,4-phenylenedisulfonyloxyimide compound and the 1,4-phenylenedisulfonyloxyimide compound generate an acid upon irradiation with radiation as described above, and thus are useful as a photoacid generator for a chemically amplified resist material. In particular, the 1,4-phenylenedisulfonamide derivative represented by the above formula (1) has a suitable transparency to an ArF excimer laser and a KrF excimer laser, and thus is suitable as the photooxidant. If the transparency is too low, the efficiency of acid generation by irradiation light is reduced, and the sensitivity is reduced.On the other hand, if the transparency is too high, sufficient irradiation light does not reach the lower layer of the resist and the pattern is trapezoidal. And other problems arise. The compounds of the present invention are also useful as photosensitive reagents in applications utilizing photoreactions, such as photolithography and printing plate materials, in addition to resist materials.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described more specifically by way of examples.

[I] Synthesis of 1,4-phenylenedisulfonamide derivative Example 1; 5- (2-methylcyclopentane-1,3-
Synthesis of dione) 2-methyl-1,4-phenylenedimethanesulfonamide (hereinafter referred to as “MM-Ms”) (1) Synthesis of 2-methyl-1,4-phenylenedimethanesulfonamide 9.734 g (44.2 mol) of 2-methyl-1,4-phenylenediamine sulfate was dissolved in water, and 3.504 g of NaOH pellets (8.76 g) were dissolved.
× 10 ^-2 mol) and neutralized. Further, 50 ml of a 20% by weight aqueous solution of NaOH was added to make the system alkaline, and the system was cooled in a cold water bath with stirring. Then
Methanesulfonyl chloride 10 ml (1.29 × 10
^-4 mol) was added dropwise over 30 minutes. 3 after the end of dripping
After 0 minute, a 10% aqueous solution of H ₂ SO ₄ was added to make the inside of the system acidic, and the formed white precipitate was filtered off from the reaction solution and redissolved in alkaline water. Add activated charcoal here and add 130
After stirring at 1 ° C. for 1 hour, the mixture was filtered into glacial acetic acid and recrystallized to obtain 96 g of 2-methyl-1,4-phenylenedimethanesulfonamide as white needle crystals (yield 70%). .

The IR spectrum data of the obtained compound is shown below. IR; (cm ^-1 ) 3430,1555 (-NH-) 3959, 1495 (aromatic ring having a substituent at 1, 2, 4 position) 1305, 1140 (S = O) 1200 (-CN-) 1305 ~ 1310 (Ar-NH)

(2) Synthesis of 2-methyl-1,4-phenylenedimethanesulfonimide 2-methyl-1,4-phenylene obtained by the above step (1)
0.991 g of phenylenedimethanesulfonamide (3.
78 × 10 ⁻³ mol) was dissolved in 25 ml of glacial acetic acid in a reaction vessel under a nitrogen atmosphere, and 1.693 of lead tetraacetate was dissolved.
g. After stirring for 6 hours, 0.3 ml of ethylene glycol was added to inactivate the lead tetraacetate. Then, filtration and purification were performed to obtain 0.1 g of 2-methyl-1,4-phenylenedimethanesulfonimide as yellow powdery crystals.

The IR spectrum data of the obtained compound was
It is shown below. IR; (cm^-11305, 1140 (S = O) 1560 (-C = N-) The starting material 2-methyl-1,4-phenylenedimethane
Of the absorption observed for the sulfonamide, 3430
cm^-1(-NH-), 3050, 1495cm ^-1(1,
Aromatic ring having substituents at positions 2 and 4), 1200 cm^-1(-
CN-), 1305 to 1310 cm^-1(Φ-NH)
Absorption disappeared.

(3) Synthesis of MM-Ms In a reaction vessel, 2-methylcyclopentane-1,
0.114 g (1.015 × 10 ⁻³ mol) of 3-dione
Was dissolved in 25 ml of water, and 0.5 equivalent of sodium methoxide was added. Next, while stirring at room temperature, 0.200 g (8.91 g) of 2-methyl-1,4-phenylenedimethanesulfonimide obtained in the step (2) was obtained.
× 10 ^-4 mol) in 25 ml of water.
It was added dropwise over 0 minutes. After stirring for 1 hour from the end of the dropwise addition, the mixture was filtered and purified by a column fractionation method to obtain 0.31 g of MM-Ms having a structure represented by the following formula (3) as a powder (yield almost 100%). . This compound was found to have a melting point of 226.2 ° C and a thermal decomposition point of 257.8 ° C, as measured by differential scanning calorimetry.

[0028]

Embedded image

The IR spectrum data of the obtained MM-Ms is shown below, and its chart is shown in FIG. IR; (cm ^-1 ) 3460,1555 (-NH-) 1740,865 (aromatic ring having a substituent at the 1,2,4,5-position) 1305,1150 (S = O) 1305 to 1315 (Ar-NH) ) 1210 (-CN-)

The MM-Ms was evaluated for ultraviolet transmittance. That is, 0.03046 g of MM-Ms was dissolved in 10 ml of acetonitrile, and the ultraviolet absorption spectrum was measured. The result is shown in FIG. This MM-M
s at 193 nm has an ultraviolet absorption of 0.673, a maximum absorption wavelength λmax of 210 nm, and a molar absorption coefficient ε of 858.
3.0.

Further, the photoreactivity (acid generating ability) of the MM-Ms was evaluated. That is, MM-Ms is 1.96 ×
10 ^-3 mol / l, TBPBNa (Tetra-Bromophenol
Acetonitrile solution containing Blue Na) at a concentration of 9.31 × 10 ⁻⁴ mol / l was prepared, and this solution was irradiated with a low-pressure mercury lamp to observe the change over time in its absorption spectrum. The result is shown in FIG. Since the absorption at 620 nm due to the quinoid structure gradually decreases as the irradiation time becomes longer, it can be seen that acid is generated from MM-Ms by irradiation with ultraviolet rays.

Example 2 Synthesis of 5- (2-methylcyclopentane-1,3-dione) 2-methyl-1,4-phenylenetetramethanesulfonamide (hereinafter referred to as "MS.5") Reaction vessel MM-Ms obtained in Example 1
0.5 g (2.170 × 10 ⁻³ mol) is dissolved in 10 ml of pyridine, and 1 ml of methanesulfonyl chloride is dissolved.
(1.292 × 10 ^-2 mol) in a nitrogen atmosphere for 30
It was added dropwise over a period of minutes. When the stirring was continued for 24 hours after the completion of the dropping, the color of the solution changed from colorless to red. afterwards,
The pyridine in the system was removed by evaporation, and recrystallization was performed using chloroform. 5 0.24 g was obtained (yield 24.6%).

[0033]

Embedded image

This MS. The photoreactivity (acid generating ability) of each of the samples No. 5 was evaluated. That is, MS. 5 to 1.52 × 10
^-5 mol / l, 1.82 × 10 ^-6 mol of TBPBNa
An acetonitrile solution was prepared at a concentration of / l, and the solution was irradiated with a low-pressure mercury lamp to observe the change over time in its absorption spectrum. FIG. 4 shows the results. As the irradiation time becomes longer, the absorption at 620 nm due to the quinoid structure decreases. 5
From this, it can be seen that acid is generated.

Example 3 5- (2-methylcyclopentane-1,3-dione) 2-methyl-1,4-phenylenedicamphorsulfonamide (hereinafter "MM-Cmp")
That. (1) Synthesis of 2-methyl-1,4-phenylenediamine 2.071 g (9.08 × 10 ⁻³ mol) of 2-methyl-1,4-phenylenediamine sulfate was mixed with 30 ml of ethyl acetate and 15 ml of water. Was added, and 0.962 g (2.18 × 10 ^-2 mol) of NaOH pellets were further added, followed by extraction with a separating funnel. This operation was repeated four times with respect to the separated ethyl acetate layer, and then ethyl acetate was distilled off.
1.09 g of -methyl-1,4-phenylenediamine was obtained (yield 98%).

The IR spectrum data of the obtained compound is shown below. IR; (cm ^-1 ) 3400, 1610, 860 (-NH ₂ ) 1160, 1090, 1040, 805, 700 (1,
Aromatic ring having a substituent at 2,4-position) 1305, 1140 (S = O) 1220 (-CN-)

(2) Synthesis of 2-methyl-1,4-phenylenedicamphorsulfonamide 2-methyl-1,4-phenylene obtained by the above step (1)
1.1095 g of phenylenediamine (9.08 × 10 ⁻³⁾
mol) was dissolved in 33 ml of pyridine, and (IS)-(+)-10-
4.732 g of camphage sulfonyl chloride (1.
89 × 10 ^-2 mol) in 13 ml of pyridine was added. After stirring for 12 hours, the reaction solution was poured into an aqueous HCl solution, and the formed brown precipitate was separated by filtration. This precipitate was redissolved in glacial acetic acid and cooled, and the formed precipitate was separated by filtration to obtain 1.38 g of 2-methyl-1,4-phenylenedicamphorsulfonamide as white powdery crystals (yield 23). 0.7%).

The IR spectrum data of the obtained compound is shown below. IR; (cm ^-1 ) 3430, 1560 to 1555 (-NH-) 1740 (-C = O) 2950 (-CH ₃ ) 1330, 1140 1200 (-CN-)

(3) Synthesis of 2-methyl-1,4-phenylenedicamphorsulfonimide 2-methyl-1,4-phenylene obtained by the above step (2)
0.991 g of phenylene camphorsulfonamide
(1.80 × 10 ⁻³ mol) was dissolved in 25 ml of glacial acetic acid, and 1.732 g of lead tetraacetate was added. After stirring for 8 hours, a small amount of ethylene glycol was added to inactivate the lead tetraacetate. The reaction solution was concentrated and then cooled, and the generated crystals were separated by filtration and dried to give 2-methyl-1,4-phenylenedicamphorsulfonimide in a yield of 50%.
Obtained as a yellow powder.

The IR spectrum data of the obtained compound is shown below. IR; (cm ^-1 ) 1330 (S = O) 1740 (-C = O) 1560 (-C = N-) Absorption observed in raw material 2-methyl-1,4-phenylenedicamphorsulfonamide Of which, 34
30, 1560-1555 cm ^-1 (-NH-) and 1
The absorption at 200 cm ^-1 (-CN-) disappeared.

(4) Synthesis of MM-Cmp 2-methylcyclopentane-1,3-dione 0.154
g (9.11 × 10 ⁻⁴ mol) was dissolved in 20 ml of water, and 0.5 equivalent of sodium methoxide was added. Then, while stirring at room temperature, 0.200 g (9.11 × 10 ⁻⁴ mol) of 2-methyl-1,4-phenylenedicamphorsulfonimide obtained in the above step (3) is dissolved in 30 ml of water. The resulting aqueous solution was added dropwise. here,
A small amount of sodium methoxide was added in three portions as the dropwise addition proceeded so as to maintain the pH of the reaction solution on the acidic side. After stirring for 1 hour from the end of the dropwise addition, the mixture was filtered and purified by a column fractionation method to obtain MM-Cmp having a structure represented by the following formula (5) as a white powder in a yield of 80%.

[0042]

Embedded image

The IR spectrum data of the obtained MM-Cmp is shown below, and its chart is shown in FIG. IR; (cm ^-1 ) 3460, 1560 (-NH-) 1740 (C = O) 1305, 1150 (S = O) 1200 (-CN-)

The UV transmittance of this MM-Cmp was evaluated. That is, MM-Cmp 0.06684 g
Was dissolved in 10 ml of acetonitrile, and its ultraviolet absorption spectrum was measured. FIG. 6 shows the result. This MM
-The maximum absorption wavelength λmax1 of Cmp is 204 nm (absorbance 0.539), and the maximum absorption wavelength λmax2 is 239.9 nm.
(Absorbance: 0.208).

Further, the photoreactivity (acid generating ability) of the MM-Cmp was evaluated. That is, MM-Cmp is set to 2.5
3 × 10 ⁻⁶ mol / l, 9.31 × 10 9 TBPBNa
^An acetonitrile solution containing a concentration of ^-4 mol / l was prepared, and this solution was irradiated with a low-pressure mercury lamp, and the change over time in the absorption spectrum was observed. FIG. 7 shows the result. 620 due to kinoid structure as irradiation time increases
Since the absorption in nm gradually decreases, it can be seen that acid is generated from MM-Cmp by irradiation of ultraviolet rays.

[II] Synthesis of 1,4-phenylenedisulfonyloxyimide compound Example 4 Synthesis of 1,4-phenylenedimethanesulfonyloxyimide 3.00 g of benzoquinonedioxime (2.17 × 10 ^-2)
mol) was dissolved in 40 ml of pyridine, and the inside of the system was kept at 0 ° C by an ice bath. Here, 5.7 ml (4.78 × 10 ^-2 mol) of methanesulfonyl chloride was added to pyridine 1
A solution dissolved in 0 ml was slowly added dropwise. After stirring for 12 hours, the reaction solution was poured into an aqueous HCl solution, the solid content was separated by filtration, and the mixture was purified by a chromatogram fractionation method to obtain 1,4-phenylenedimethanesulfonate having a structure represented by the following formula (6). 3.81 g of roxyimide was obtained as a yellow powder (yield 82%).

[0047]

Embedded image

The IR spectrum data of the obtained 1,4-phenylenedimethanesulfonyloxyimide is shown below, and the chart is shown in FIG. IR; (cm ^-1 ) 1315, 1120 (S = O) 1570 (-C = N-) Among the absorptions observed in the starting benzoquinone dioxime, 3500 cm ^-1 (-OH) and 1675
The absorption at cm ^-1 (-C = N-OH) disappeared.

Further, the photoreactivity (acid generating ability) of the 1,4-phenylenedimethanesulfonyloxyimide was evaluated. That is, 3.54 × 10 ⁻⁶ mol / l of 1,4-phenylenedimethanesulfonyloxyimide, TBPBN
A solution of acetonitrile containing a at a concentration of 8.99 × 10 ⁻⁴ mol / l was prepared, and this solution was irradiated with a low-pressure mercury lamp, and the change over time in its absorption spectrum was observed. FIG. 9 shows the result. Since the absorption at 620 nm due to the quinoid structure gradually decreases as the irradiation time becomes longer, it can be seen that acid is generated from 1,4-phenylenedimethanesulfonyloxyimide by irradiation with ultraviolet rays.

Example 5 Synthesis of 1,4-phenylenedicamphorsulfonyloxyimide 0.824 g of benzoquinone dioxime (6.10 × 10
^-3 mol) was dissolved in 40 ml of pyridine, and the inside of the system was kept at 0 ° C. with an ice bath. A solution in which 3.02 g (1.20 × 10 ⁻² mol) of camphorsulfonyl chloride was dissolved in 30 ml of pyridine was slowly added dropwise thereto.
After stirring for 13 hours, the reaction solution was poured into an aqueous HCl solution, the solid content was separated by filtration, and the resultant was purified by a column separation method.
2.32 g of 1,4-phenylenedicamphorsulfonyloxyimide having a structure represented by the following formula (7) was obtained as a yellow powder (yield: 67%).

[0051]

Embedded image

The IR spectrum data of the obtained 1,4-phenylenedicamphorsulfonyloxyimide is shown below, and the chart is shown in FIG. IR; (cm ^-1 ) 1300, 1180 (S = O) 1560 (-C = N-) 1760 (-C = O) 2995 (-CH ₃ ) Note that, among the absorptions observed in the raw material benzoquinone dioxime, , 3500 cm ^-1 (-OH) and 1675
The absorption at cm ^-1 (-C = N-OH) disappeared.

Further, the photoreactivity (acid generating ability) of the 1,4-phenylenedicamphorsulfonyloxyimide was evaluated. That is, 1,4-phenylene camphorsulfonyloxyimide was converted to 2.60 × 10 ⁻⁶ mol / l, T
An acetonitrile solution containing BPBNa at a concentration of 9.31 × 10 ⁻⁴ mol / l was prepared, and the solution was irradiated with a low-pressure mercury lamp to observe the change over time in its absorption spectrum. The result is shown in FIG. Since the absorption at 620 nm due to the quinoid structure gradually decreases as the irradiation time becomes longer, it can be seen that acid is generated from 1,4-phenylenedimethanesulfonyloxyimide by irradiation with ultraviolet rays.

Example 6 Synthesis of 1,4-phenylenedi-p-toluenesulfonyloxyimide 1.381 g of benzoquinone dioxime (1.02 × 10
^-2 mol) was dissolved in 40 ml of pyridine, and the system was kept at 0 ° C with an ice bath. A solution in which 4.248 g (2.23 × 10 ⁻² mol) of p-toluenesulfonyl chloride was dissolved in 30 ml of pyridine was slowly added dropwise thereto. After stirring for 12 hours, the reaction solution was poured into an aqueous HCl solution, the solid content was separated by filtration, and the solid was purified by a column separation method to obtain 1,4-phenylenediamine having a structure represented by the following formula (8).
p-Toluenesulfonyloxyimide was obtained at a yield of 70%.

[0055]

Embedded image

The IR spectrum data of the obtained 1,4-phenylenedi-p-toluenesulfonyloxyimide is shown below, and the chart is shown in FIG. Analysis result IR; (cm ^-1 ) 1300, 1180 (S = O) 1560 (-C = N-) 3075 (tert-Butyl) 1100 (p-substituted aromatic ring) It is found in the raw material benzoquinone dioxime. 3500 cm ^-1 (-OH) and 1675
The absorption at cm ^-1 (-C = N-OH) disappeared.

Thus, it was found that all of the compounds obtained in Examples 1 to 5 had a function of generating an acid upon irradiation with radiation. In particular, the compound of the present application is suitable as a photoacid generator in a chemically amplified resist material for an ArF excimer laser since the molar extinction coefficient ε with respect to an ArF excimer laser (193 nm) is in an appropriate range.

It should be noted that the present invention is not limited to the specific embodiments described above, but may be variously modified within the scope of the present invention in accordance with the purpose and application.

[0059]

According to the present invention, a novel 1,4-phenylenedisulfonamide derivative and a 1,4-phenylenedisulfonyloxyimide compound which generate an acid upon irradiation with radiation such as ArF excimer laser and KrF excimer laser Is provided. These compounds can be used as a photo-oxidizing agent of a chemically amplified resist material. In particular, the 1,4-phenylenedisulfonamide derivative of the present invention has an appropriate transparency to an ArF excimer laser and a KrF excimer laser, and is therefore useful as the photoacid generator.

[Brief description of the drawings]

FIG. 1 is a chart showing an IR spectrum of a compound obtained in Example 1.

FIG. 2 is a chart showing a UV absorption spectrum of the compound obtained in Example 1.

FIG. 3 is a characteristic diagram showing a change in UV spectrum when the compound obtained in Example 1 is irradiated with radiation.

FIG. 4 is a characteristic diagram showing a change in UV spectrum when the compound obtained in Example 2 is irradiated with radiation.

FIG. 5 is a chart showing an IR spectrum of the compound obtained in Example 3.

FIG. 6 is a chart showing a UV absorption spectrum of the compound obtained in Example 3.

FIG. 7 is a characteristic diagram showing a change in UV spectrum when the compound obtained in Example 3 is irradiated with radiation.

FIG. 8 is a chart showing an IR spectrum of the compound obtained in Example 4.

FIG. 9 is a characteristic diagram showing a change in UV spectrum when the compound obtained in Example 4 is irradiated with radiation.

FIG. 10 is a chart showing an IR spectrum of the compound obtained in Example 5.

FIG. 11 is a characteristic diagram showing a change in UV spectrum when the compound obtained in Example 5 is irradiated with radiation.

FIG. 12 is a chart showing an IR spectrum of the compound obtained in Example 6.

Claims (2)

[Claims] 1. A 1,4-phenylene compound represented by the following formula (1):
Range sulfonamide derivatives. Embedded image[Wherein, R¹Is a hydrogen atom, a C 1-4 linear or
Branched alkyl group or -SO_TwoR^TwoOrganic group represented by
And R^TwoRepresents a linear, branched or C1-C12
Is a cyclic alkyl group, a group represented by the following formula (1a),
Or p-R^s1-C ₆H_Four-(However, R^{s 1}Is 1 to 4 carbon atoms
Is a linear or branched alkyl group. ) Indicates a group
You. Embedded image] 2. A 1,4-phenylenedisulfonyloxyimide compound represented by the following formula (2). Embedded image Wherein, R ³ represents a linear 1 to 12 carbon atoms, branched or cyclic alkyl group, a group represented by the following formula (2a) or _{^{p-R s2 -C 6 H 4}} , - ( provided that R ^s2 has 1 to 4 carbon atoms
Is a linear or branched alkyl group. ) Represents a group. Embedded image ]