JP2704318B2 - Photosensitive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to lithographic printing, proof printing for multicolor printing, drawings for overhead projectors, and positive resists capable of forming fine resist patterns when manufacturing integrated circuits of semiconductor devices. A photosensitive composition.

[0002]

2. Description of the Related Art Orthoquinonediazide compounds are conventionally known as positive-acting photosensitive substances which are solubilized by actinic rays in applications such as lithographic printing plates, and have been widely used in lithographic printing plates. Was. Examples of such orthoquinonediazide compounds are described in, for example, U.S. Pat.Nos. 2,766,118, 2,677092, 2,277,972, and 28.
59112, 2907665, 3046110, 3046111
Nos. 3046115, 3046118, 3046119, 30
No. 46120, No. 3046121, No. 3046122, No. 3046123
Nos. 3061430, 3102809, 3106465, 36
It is described in numerous publications, including the specifications of 35709 and 3647443.

[0003] These orthoquinonediazide compounds are:
It utilizes the fact that it is decomposed by irradiation with actinic rays to produce a 5-membered carboxylic acid and becomes alkali-soluble, but all have the disadvantage of insufficient photosensitivity.

Various attempts have been made to enhance the photosensitivity of a photosensitive composition containing an orthoquinonediazide compound, but it has been extremely difficult to increase the photosensitivity while maintaining the development tolerance during development. Was difficult. For example, as an example of such an attempt, Japanese Patent Publication No. 48-1224
No. 2, JP-A-52-40125, U.S. Pat.
The contents described in the specification such as No. 3 can be cited.

As a new photosensitive material acting positively, a disulfone compound is disclosed in JP-A-2-100,053 and JP-A-2-100,053.
No. 055. These dissociate the disulfone group upon exposure to generate twice as much sulfinic acid or sulfonic acid, but are not suitable for longer wavelength light sources such as g-line (436 nm) and i-line (365 nm). However, there is a problem that the sensitivity is not sufficient depending on the light source.

On the other hand, as a positive photoresist composition, a composition containing an alkali-soluble resin and a naphthoquinonediazide compound as a photosensitive material is generally used. For example, US Pat. No. 3,666,473 as “Novolak-type phenolic resin / naphthoquinonediazide-substituted compound”
And U.S. Pat. Nos. 4,115,128 and 4,173,470, as well as the most typical compositions of "novolak resin composed of cresol-formaldehyde / trihydroxybenzophenone-1,2-naphthoquinonediazide sulfonate". An example is Thompson's "Introduction Too Microlithography" (LF Thompson
"Introduction to Microlithography") (ACS Publishing, No. 219, pp. 112-121).

[0007] The novolak resin as a binder can be dissolved in an aqueous alkali solution without swelling, and when used as a mask for etching, gives a particularly high resistance to plasma etching. Especially useful for: Also, the naphthoquinonediazide compound used in the photosensitive material itself acts as a dissolution inhibitor that reduces the alkali solubility of the novolak resin, but when decomposed by irradiation with light, generates an alkali-soluble substance, and rather increases the alkali solubility of the novolak resin. It is unique in that it acts to enhance it, and is particularly useful as a photosensitive material for a positive photoresist because of its large property change to light.

From this point of view, many positive photoresists containing a novolak resin and a naphthoquinonediazide-based photosensitive material have been developed and put into practical use.
Sufficient results have been achieved in line width processing down to about μm.

[0009] However, the degree of integration of integrated circuits is increasing more and more, and in the manufacture of semiconductor substrates such as VLSI, 1 μm is required.
Processing of an ultrafine pattern having a line width of m or less has been required. In such applications, particularly high resolution, a photoresist having high sensitivity from the viewpoint of high pattern shape reproduction accuracy that accurately captures the shape of the exposure mask and high productivity is required, and the conventional positive photoresist described above is required. In fact, it is not possible to respond.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel photosensitive composition which solves these problems. That is, it is to provide a novel photosensitive composition having high sensitivity.

Still another object of the present invention is to provide a positive photosensitive composition having a high resolution and capable of processing an ultrafine pattern having a line width of 1 μm or less.

[0012]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that the above object can be achieved by using a novel positive photosensitive composition. The invention has been reached.

That is, the present invention provides a positive photosensitive composition containing a compound having a 1,2-naphthoquinone-2-diazide-4- and / or 5-disulfonyl group represented by the following general formula (I): Is provided.

A— (SO ₂ —SO ₂ —D) n (I) wherein D is 1,2-naphthoquinone-2-diazide-4
-Yl group or 1,2-naphthoquinone-2-diazide-5
A represents an -yl group, A represents an n-valent aliphatic or aromatic hydrocarbon group, and n represents an integer of 1 or more.

A preferably represents an aliphatic group having 1 to 30 carbon atoms or a monocyclic or polycyclic aromatic group having 6 to 20 carbon atoms which may have a substituent. Preferred substituents include alkyl, aryl, alkoxy, nitro,
Examples include a cyano, amide, ureido, urethane group or halogen atom. Further, A may contain a divalent group such as ketone, ether, ester, amide, urethane and ureide.

Preferred values of n are integers from 1 to 10,
More preferably, it is an integer of 1 to 5.

The compound of the general formula (I) used in the present invention can increase the suitability for a light source in a wide range by combining different kinds of photosensitive groups (namely, naphthoquinonediazide group and disulfone group), thereby increasing the sensitivity. It is intended.

Hereinafter, the components of the present invention will be described in detail. [Compound represented by the formula (I) ] The compound represented by the general formula (I) is described in GC Denser, Jr. et al., Journal of O.D.
rganic Chemistry, 31 , 3418-3419 (196
6) The method described by TP Hilditch, Journal of Chemic
al Society, 93 , 1524-1527 (1908), or by O. Hinsberg, Berichte der Deu
tschen Chemischen Gesellschaft, 49 , 2593-2
594 (1916) can be synthesized. That is, in a sulfuric acid aqueous solution, cobalt (III) sulfate
A method of synthesizing from a sulfinic acid represented by the general formula (II) or (III), a method of synthesizing from a sulfonic acid chloride represented by the general formula (IV) or (V) using ethyl xanthate, or a base Under lipophilic conditions, for example, a method of reacting a sulfinic acid represented by the general formula (II) with a sulfonic acid chloride represented by the general formula (V) to synthesize the compound is exemplified.

A- (SO ₂ H) _n (II) D-SO ₂ H (III)

A- (SO ₂ Cl) _n (IV) D-SO ₂ Cl (V) (where A and D have the same meanings as A and D defined in the general formula (I).)

Hereinafter, specific compounds represented by formula (I) used in the present invention will be exemplified.

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[1,2-Naphthoquinone-2-diazide-
4- and / or 5-sulfonic acid ester compound] The positive photosensitive composition of the present invention may contain, if necessary, a compound of the present invention represented by the formula (I) and another 1,2-naphthoquinone-2- compound. A diazide-4- and / or 5-sulfonic acid ester compound may be added and used in combination. Such 1,2
The -naphthoquinone-2-diazide-4- and / or 5-sulfonic acid ester compound is generally a mono- or a 1,2-naphthoquinone-2-diazide compound having a halogenosulfonyl group such as sulfonyl chloride at the 4- or 5-position. It can be represented as a sulfonylate compound obtained by condensation with a polyhydroxyphenyl compound. Typical examples of such a mono- or polyhydroxyphenyl compound are benzophenone compounds having a hydroxy group. For example, 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone,
2,2'-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,4,4 ' Trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydrobenzophenone, In addition to 3,3 ', 4,4'-tetrahydroxybenzophenone, benzophenone having 5 or more hydroxy groups as shown in JP-A-62-150245, and derivatives thereof are included. Furthermore, p-cresol, p-
t-butylphenol, resorcinol, pyrogallol,
2,2'-dihydroxybiphenyl, 2,2 ', 4
Hydroxy group-substituted biphenyl compounds such as 4'-tetrahydroxybiphenyl can also be mentioned.

Still further, relatively high molecular weight compounds such as phenol-formaldehyde resins or o-, m-, or p-cresol-formaldehyde resins described in US Pat. No. 3,046,120 can be used in the present invention. .

Also, Japanese Patent Application Laid-Open No. Sho 56-1045,
JP-A-56-1044, JP-B-43-28403
Condensates of polyhydric phenols with aldehydes and ketones disclosed in JP-A-59-84361 and JP-B-49-24361.
No. 239, aldehydes of catechol, resorcin, or hydroquinone with substituted phenols.
Co-condensates with ketones, condensates of substituted phenols and benzaldehydes described in JP-A-60-31138, and aldehydes and ketones of phenols with substituted phenols such as o-, m- or p-cresol The co-condensate, p-hydroxystyrene polymer and the like are also effectively used in the present invention.

When used in combination with the compound of the present invention represented by the general formula (I), the compound of the general formula (I) and the 1,2-
The ratio of the naphthoquinone-2-diazide-4- and / or 5-sulfonate compound is 10: 1 to 1: 1 by weight.
20, preferably 5: 1 to 1:10, more preferably 2: 1 to 1: 5.

[Alkali-Soluble Resin] The positive photosensitive composition of the present invention preferably contains an alkali-soluble resin in order to make the alkali solubility of the exposed portion more efficient and to impart film properties and heat resistance. Add and use.

Such an alkali-soluble polymer is preferably a phenolic hydroxyl group, a carboxylic acid group, a sulfonic acid group, an imide group, a sulfonamide group, an N-sulfonylamido group, an N-sulfonylurethane group, an active methylene group, or the like. It is a polymer having an acidic hydrogen atom having a pKa of 11 or less. Suitable alkali-soluble polymers include novolak-type phenol resins, specifically phenol-formaldehyde resins, o-cresol-formaldehyde resins,
There are m-cresome-formaldehyde resin, p-cresome-formaldehyde resin, xylenol-formaldehyde resin, and co-condensates thereof. Further, as described in JP-A-50-125806, together with the above-mentioned phenol resin, phenol or cresome substituted with an alkyl group having 3 to 8 carbon atoms, such as t-butylphenol formaldehyde resin, and formaldehyde. And a condensate thereof. Also N-
Polymers containing a phenolic hydroxy group-containing monomer such as (4-hydroxyphenyl) methacrylamide as a copolymer component, p-hydroxystyrene, o-hydroxystyrene, m-isopropenylphenol, p-isopropenylphenol or the like alone or Copolymerized polymers and also partially etherified and partially esterified polymers of these polymers can be used.

Further, a polymer containing a carboxyl group-containing monomer such as acrylic acid or methacrylic acid as a copolymer component,
Polymers obtained by hydrolyzing or half-esterifying a copolymer of maleic anhydride and styrene with an alcohol, a carboxyl group-containing polyvinyl acetal resin described in JP-A-61-267042, and a carboxyl group described in JP-A-63-124047 Contained polyurethane resins can also be suitably used.

Further, a polymer containing N- (4-sulfamoylphenyl) methacrylamide, N-phenylsulfonylmethacrylamide, maleimide as a copolymer component and an active methylene group-containing polymer described in JP-A-63-127237 are also included. Can be used.

These alkali-soluble polymers can be used alone or as a mixture of several kinds.
A preferable addition amount in the photosensitive composition is 30 to 99% by weight, preferably 50 to 97% by weight based on the total solid content of the photosensitive composition.
%, More preferably in the range of 60 to 95% by weight.

[Other Preferred Components] The positive photosensitive composition of the present invention further contains, if necessary, a dye, a pigment, a plasticizer, a compound for increasing photolysis efficiency (a so-called sensitizer), and the like. Can be done.

Dyes can be used as colorants, but suitable materials include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 130, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603,
Oil Black BY, Oil Black BS, Oil Black T-505 (or more, Orient Chemical Industries, Ltd.)
Manufactured), Crystal Violet (CI42555), Methyl Violet (CI42535), Rhodamine B
(CI45170B), malachite green (CI42
000), methylene blue (CI52015) and the like.

A printing agent for obtaining a visible image immediately after exposure can be added. As such a baking agent, a combination of a photosensitive compound that releases an acid upon exposure and an organic dye capable of forming a salt can be exemplified. Specifically, JP-A-50-36209, 5
Combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and salt-forming organic dyes described in JP-A-3-8128 and JP-A-53-36223 and JP-A-54-747.
Combinations of a trihalomethyl compound and a salt-forming organic dye described in No. 28 can be mentioned.

In the composition of the present invention, a cyclic acid anhydride, another filler or the like can be added to further enhance the sensitivity. As the cyclic acid anhydride, U.S. Pat.
Phthalic anhydride, as described in JP, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴ - tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic acid anhydride, chlorosulfonic maleic anhydride , Α-phenyl maleic anhydride, succinic anhydride, pyromellitic acid and the like. By containing these cyclic acid anhydrides in an amount of 1 to 15% by weight based on the solid content of the whole composition, the sensitivity can be increased up to about three times.

[Solvent] The positive photosensitive composition of the present invention is
When used as a material for lithographic printing, the above components are dissolved in a solvent capable of dissolving and applied onto a support. For resist materials such as semiconductors, they are used as dissolved in a solvent. As the solvent used herein, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 2-ethoxyethyl Acetate, 1-methoxy-2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ- Butyrolactone, toluene,
There are ethyl lactate and the like, and these solvents are used alone or as a mixture. The concentration (total solid content including additives) in the above components is 2 to 50% by weight. In addition, when used by coating, the amount of coating varies depending on the application, for example, regarding photosensitive lithographic printing plates, generally, as a solid content
0.5-3.0 g / m ² is preferred. The photosensitivity increases as the coating amount decreases, but the physical properties of the photosensitive film deteriorate.

[ Production of a lithographic printing plate] In the case of producing a lithographic printing plate using the positive photosensitive composition of the present invention, examples of the support include paper and plastics (polyethylene, polypropylene, polystyrene, etc.). , Laminated paper, metal plates such as aluminum (including aluminum alloy), zinc, copper, etc., cellulose acetate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, Examples include plastic films such as polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, and the like, and metal or laminated paper or plastic films as described above. Among these supports, the aluminum plate is particularly preferable because it is extremely dimensionally stable and inexpensive. Further, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable. Mechanical method such as wire brush graining, brush graining, ball graining, solution honing, buff graining, etc., HF, AlCl ₃ Graining the surface by chemical graining using HCl or HCl as an etchant, electrolytic graining using nitric acid or hydrochloric acid as an electrolytic solution, or composite graining performed by combining these surface roughening methods. Anodizing with acid or alkali, followed by anodic oxidation with a DC or AC power supply in sulfuric acid, phosphoric acid, oxalic acid, boric acid, chromic acid, sulfamic acid or a mixed acid thereof to provide a strong passive film on the aluminum surface Are preferred. Although the aluminum surface is hydrophilized by such a passivation film itself, if necessary, US Pat.
No. 3,118,461 (sodium silicate, potassium silicate); U.S. Pat. Molybdate treatment, alkyl titanate treatment described in British Patent No. 1108559, polyacrylic acid treatment described in German Patent No. 1,091,433, described in German Patent No. 1,130,393 and British Patent No.1230447. Polyvinylphosphonic acid treatment, phosphonic acid treatment described in JP-B-44-6409, phytic acid treatment described in U.S. Pat. No. 3,307,951, JP-A-58-16893, 58-1
No. 8291, an undercoating treatment with a complex of a hydrophilic organic polymer compound and a divalent metal ion;
Particularly preferred are those subjected to a hydrophilization treatment with an undercoat of a water-soluble polymer having a sulfonic acid group described in -101651. Other hydrophilic treatment methods include silicate electrodeposition described in US Pat. No. 3,866,662.

Further, those subjected to graining treatment, anodic oxidation and sealing treatment are also preferable. Such a sealing treatment is performed by immersion in hot water and a hot aqueous solution containing an inorganic salt or an organic salt, a steam bath or the like.

[Active Light or Radiation] As the light source of the active light used for exposure of the photosensitive composition of the present invention,
There are mercury lamps, metal halide lamps, xenon lamps, chemical lamps, carbon arc lamps and the like. Examples of the radiation include an electron beam, an X-ray, an ion beam, and far ultraviolet rays.
Preferably, the light source for the photoresist is g-line, i-line.
Line, Deep-UV light is used. Scanning or pulse exposure using a high-density energy beam (laser beam or electron beam) can also be used in the present invention. Examples of such a laser beam include a helium / neon laser, an argon laser, a krypton ion laser, a helium / cadmium laser, and a KrF excimer laser.

[Developer] As a developer for the positive photosensitive composition of the present invention, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium tertiary phosphate, sodium dibasic phosphate, Aqueous solutions of inorganic alkali agents such as ammonium tertiary phosphate, ammonium diphosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia and organic alkali agents such as tetraalkylammonium OH salts are suitable. Is added so as to be 0.1 to 10% by weight, preferably 0.5% by weight.

Further, an organic solvent such as a surfactant or alcohol can be added to the alkaline aqueous solution, if necessary.

[0050]

The present invention will be described below in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited thereto.

Synthesis Example Synthesis of p-chlorophenyl-1,2-naphthoquinone-2-diazido-5-disulfone (Compound Example I-2): 189 g of sodium sulfite was dissolved in 600 ml of water and 60 to 7
After heating to 0 ° C and adding 63 g of p-chlorobenzenesulfonyl chloride, the mixture was reacted at 50 to 60 ° C for 5 hours. After filtering off insolubles, the reaction solution was returned to room temperature and concentrated hydrochloric acid was added to make the reaction system acidic. The deposited precipitate was collected by filtration and p-
52 g of chlorobenzenesulfinic acid were obtained.

15 ml of water was added to 8.8 g of p-chlorobenzenesulfinic acid, and a solution prepared by dissolving 2 g of sodium hydroxide in 5 ml of water was added. While stirring this solution at room temperature, a solution in which 13.5 g of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride was dissolved in 40 ml of THF was added, and the mixture was further stirred and reacted at room temperature for 24 hours. The reaction solution was poured into 300 ml of water, and the precipitate was collected by filtration and subjected to column chromatography (filler: silica gel, developing solution: hexane /
Purification with ethyl acetate = 2/1) gave a yellow powder of 7.2.
g was obtained. According to NMR, the powder was identified as Compound Example (I-2)
It confirmed that it was a structure of.

Examples 1 to 5 A 2S aluminum plate having a thickness of 0.24 mm was immersed in a 10% aqueous solution of sodium tertiary phosphate maintained at 80 ° C. for 3 minutes, degreased, grained with a nylon brush, and then treated with aluminate. Etching was performed with sodium for about 10 minutes, and desmutting was performed with a 3% aqueous solution of sodium hydrogen sulfate. This aluminum plate was placed in a 20% sulfuric acid solution at a current density of 2 A / dm ² .
Anodizing was performed for a minute to prepare an aluminum plate.

The following photosensitive solutions [A] -1 to [A] -5 were prepared by changing the type of the compound represented by the general formula of the present invention used in the following photosensitive solution [A]. This photosensitive solution is applied on an anodized aluminum plate,
And dried for 2 minutes in each photosensitive lithographic printing plate [A]
-1 to [A] -5 were prepared. The coating amount at this time was 2.0 g / m ² in terms of dry weight.

Photosensitive solution [A] Cresol-formaldehyde novolak resin 1.0 g Compound of the present invention represented by the general formula (I) 0.40 g Oil blue # 603 (manufactured by Orinent Chemical Industries, Ltd.) 0.01 g Methyl ethyl ketone 5 g methyl Cellosolve 15g

The compounds of the present invention used in the photosensitive solutions [A] -1 to [A] -5 are shown in Table 1.

Next, as a comparative example, the following photosensitive solution [B] was applied in the same manner as the photosensitive solution [A] to prepare a photosensitive lithographic printing plate [B].

Photosensitive solution [B] 1,2-naphthoquinone-2-diazido-5-sulfonyl 0.40 g Esterified product of chloride and 2,3,4-trihydroxybenzophenone Cresol-formaldehyde novolak resin 1.0 g Oil blue # 603 (manufactured by Orient Chemical Industries, Ltd.) 0.01 g Methyl ethyl ketone 5 g Methyl cellosolve 15 g

The coating weight after drying was 2.0 g / m ² .
Photosensitive lithographic printing plates [A] -1 to [A] -5 and [B]
A gray scale row having a density difference of 0.15 was adhered to the photosensitive layer of No. 1 and exposed with a 2 kW high-pressure mercury lamp from a distance of 50 cm. Exposed photosensitive lithographic printing plate [A] -1 to [A] -5
And [B] were immersed and developed in DP-8 (trade name: manufactured by Fuji Photo Film Co., Ltd.) in an 8 diluted aqueous solution at 25 ° C. for 60 seconds, and the exposure time at which the fifth stage of the gray scale was completely dissolved and removed was determined. Upon measurement, the results were as shown in Table 1.

Table 1 II Example Photosensitivity The 5th stage of the gray scale of the present invention used Is the lithographic printing plate compound Exposure time to be dissolved and removed ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 1 [A]- 1 Compound Example (I-2) 35 seconds 実 施 Example 2 [A] -2 Compound Example (I-3) 40 Example 3 [A] -3 Compound Example (I-4 35} Example 4 [A] -4 Compound Example (I-18) 30} ━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 5 [A] -5 Compound Example (I-20) 25 比較 Comparative Example [B] Compound of Comparative Example 55 ━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━

The compounds of the present invention used in Examples 1 to 5 were all 1,2-naphthoquinone-2-diazide-
A 5-disulfone compound was used.

As can be seen from Table 1, the photosensitive lithographic printing plates [A] -1 to [A] -5 using the compounds of the present invention have shorter exposure time and higher sensitivity than Comparative Example [B].

Examples 6 to 9 The following photosensitive solution [C] was prepared by changing the type of the compound of the present invention.
Each type of photosensitive solution [C] -1 to [C] -4 was prepared, and 0.2 µ
Then, the mixture was filtered through a microfilter of m to prepare a resist composition.

Photosensitive solution [C] Compound of the present invention represented by the general formula (I) 0.35 g m / p = 4/6 Cresol-formaldehyde novolak resin 1.0 g Ethyl cellosolve acetate 8.5 g

The compounds of the present invention used in the photosensitive solutions [C] -1 to [C] -4 are shown in Table 2.

This resist composition was applied on a silicon wafer having an oxide film of 2500 A using a spinner and dried at 90 ° C. for 2 minutes in a convection oven under a nitrogen atmosphere to obtain a resist film having a thickness of 1.0 μm. Was. Next, exposure was performed through a test chart mask using a reduction projection exposure apparatus manufactured by Nikon Corporation, developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide for 1 minute, and rinsed with ion-exchanged water to obtain a resist pattern. Was. The resist pattern thus obtained was observed with a scanning electron microscope to evaluate the resist pattern. The sensitivity was defined as the reciprocal of the exposure amount for reproducing a 2.0 μm mask pattern, and was shown as a relative value to the sensitivity of the photosensitive solution [D] of the following comparative example. The resolving power was represented by the line width of the smallest resolved mask pattern at the exposure dose for reproducing a 2.0 μm mask pattern. Table 2 shows the results.

Photosensitive Solution [D] 0.35 g of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride Esterified product of lid and 2,3,4,4′-tetrahydroxybenzophenone Cresol-formaldehyde novolak resin 1.0 g Ethyl cellosolve acetate 8.5 g

Table 2 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example Relative resolution of the present invention using a photosensitive solution No. Compound Sensitivity (Μm) {Example 6 [C] -1 Compound Example (I-2) 1.3 0.7} Example 7 [C] -2 Compound Example (I-4) 1.3 0.7 Example 8 [C] -3 Compound Example (I-17) 1.2 0.7 Example 9 [C] -4 Compound Example (I-22) 1.4 0.7比較 Comparative Example [D] Compound of Comparative Example 1.0 0.8 ━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━

The compounds of the present invention used in Examples 6 to 9 were all 1,2-naphthoquinone-2-diazide-5.
The disulfone compound was used.

As can be seen from Table 2, the photosensitive solutions [C] -1 to [C] -4 using the compounds of the present invention have higher relative sensitivity and better resolution than Comparative Example [D].

Claims (1)

(57) [Claims] 1. A 1,2-formula represented by the following general formula (I)
A positive photosensitive composition containing a compound having a naphthoquinone-2-diazide-4- and / or 5-disulfonyl group. A- (SO ₂ -SO ₂ -D) _n (I) wherein D is 1,2-naphthoquinone-2-diazide-4
-Yl group or 1,2-naphthoquinone-2-diazide-5
A represents an -yl group, A represents an n-valent aliphatic or aromatic hydrocarbon group, and n represents an integer of 1 or more.