JPH0519480A - Positive type photoresist composition - Google Patents

Abstract

PURPOSE:To obtain the compsn. having <=0.5mum resolution and the high sensitivity and high resolution capable of meeting the trend toward the higher sensitivity in order to improve throughput by incorporating a specific compd. into this compsn. CONSTITUTION:The positive type photoresist compsn. contg. a mixture composed of the monoester substance and diester subtance obtd. by the esterification reaction of diphenols and 1,2-naphthoquinone diazidosufonyl chloride among the compds. expressed by formula I, and an alkaline-soluble resin is dissolved in a solvent to prepare a photosensitive liquid. This photosensitive liquid is applied on a substrate, such as silicone wafer, and is then dried by baking; thereafter, the coating is irradiated with radiations, such as UV rays, through a mask drawn with fine patterns, and is further baked and is developed with an aq. alkaline soln., by which the resist patterns are obtd. In the formula, X denotes-CO- or -SO2-; R1, R2 denote a hydrogen atom; the group of formula II or formula III; R denotes a hydrogen atom, halogen atom, etc.; (1) to (n)denote integer 1 to 3.

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 comprising an alkali-soluble resin and a specific 1,2-quinonediazide compound, which is sensitive to radiation such as ultraviolet rays, far ultraviolet rays, electron beams and X-rays. Particularly, the present invention relates to a positive photoresist composition suitable for producing a semiconductor circuit such as an IC.

[0002]

2. Description of the Related Art As a positive photoresist, a composition comprising an alkali-soluble resin and a naphthoquinonediazide compound having alkali-suppressing power is widely used. When this composition is irradiated with radiation, the naphthoquinonediazide compound reacts with the water in the system to form indenecarboxylic acid and becomes soluble in the alkaline developer. On the other hand, in the unexposed area, since the naphthoquinonediazide compound, which has an inhibitory effect on the alkali developing solution, is present as it is, it is difficult to dissolve in the alkali developing solution and hardly swells. As a result, a high-resolution resist pattern can be obtained. Various kinds of naphthoquinonediazide compounds having such high resolution have been developed and put into practical use, and they are often used in semiconductor manufacturing technology with a resolution of about 1 μm. However, as the degree of integration of semiconductor circuits becomes higher and higher, the required resolution becomes 0.5 μm or less, and the light source has higher resolution g-line (436n).
m) to i rays (365 nm) and deep ultraviolet rays (300 nm or less), the development of resists having sensitivity and resolution suitable for each light source is strongly desired.

On the other hand, a compound similar to the compound represented by the formula (1) in the present invention is disclosed in JP-A-2-72363.
And Japanese Patent Application Laid-Open No. 2-285351, the improvement of resolution is specified in Examples using g-line and i-line. The sensitivity is expressed as relative sensitivity when the ester of tetrahydroxybenzophenone and 1,2-naphthoquinonediazidesulfonyl chloride is 1.0. However, the improvement in sensitivity is 1.0-
Only 1.3 improvement.

[0004]

It is desired to develop a high-sensitivity, high-resolution positive photoresist composition capable of responding to a resolution of 0.5 μm or less and high sensitivity for improving throughput. ing.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that monoesters and diesters of specific diphenols and 1,2-naphthoquinonediazidesulfonyl chloride The composition of the mixture and the composition with the alkali-soluble resin is surprisingly the relative sensitivity when the sensitivity of the composition of the compound obtained by esterifying tetrahydroxybenzophenone with 1,2-naphthoquinonediazidesulfonyl chloride and the novolak resin is set to 1.0. In the present invention, it was found that the film thickness was extremely high at 1.5 to 2.5, the film loss in the unexposed area was very small, and the resolution was also very good.

That is, the present invention provides (1) a compound represented by the formula (1) wherein R ₁ or R ₂ is the formula (6) or the formula (7).
Positive to the monoester, characterized in that R _1, R ₂ contains a mixture and an alkali-soluble resin of the diester of formula (6) or (7) (may be the same or different) Type photoresist composition

[0007]

[Chemical 8]

[0008]

[Chemical 9]

[0009]

[Chemical 10]

(In the formula (1), X is --CO-- or --S
In O ₂ —, R ₁ and R ₂ may be the same or different and each represents a hydrogen atom or a group of formula (6) or (7). R
May be the same or different, hydrogen atom, halogen atom, optionally substituted alkyl group, optionally substituted alkoxy group, optionally substituted aryl group, substituted Represents an optionally substituted acyl group or an optionally substituted acyloxy group. Further, l, m, and n each represent an integer of 1 to 3, and the 6'carbon atom and the 6 "carbon atom of the benzene nucleus may be bonded via an oxygen atom.) (2) Formula (2 In the compound represented by the formula ( ₁ ), R ₁ or R ₂ is a monoester of the formula (6) or (7), and R ₁ and R ₂ are the formula (6) or the formula (7) (even if the same. (Possibly different) mixture with diester compound and alkali-soluble resin.

[0011]

[Chemical 11]

(In the formula (2), R ₁ , R ₂ , R, l,
m, n and X have the same meanings as in the above formula (1). ) (3) In the compound represented by the formula (3), R ₁ or R ₂ is a monoester of the formula (6) or the formula (7), and R ₁ and R ₂ are the formula (6) or Positive photoresist composition containing a mixture with a diester of formula (7) (which may be the same or different) and an alkali-soluble resin.

[0013]

[Chemical 12]

(In the formula (3), R ₁ , R ₂ , R, l,
m, n and X have the same meanings as in the above formula (1). ) (4) Phenols represented by formula (4) and 1,
Charge ratio (molar ratio) of 2-naphthoquinonediazide-4-sulfonyl chloride or 1,2-naphthoquinonediazide-5-sulfonyl chloride or a mixture of these 1,2-naphthoquinonediazidesulfonyl chlorides.
Positive containing a mixture of a monoester and a diester obtained by performing an esterification reaction in the range of (1: 1.95) to (1: 0.3) and an alkali-soluble resin. Type photoresist composition

[0015]

[Chemical 13]

(In the formula (4), R, l, m, n and X
Represents the same meaning as in the above formula (1). ) (5)
Phenols represented by the formula (5) and 1,2-naphthoquinonediazide-4-sulfonyl chloride or 1,2
-Naphthoquinone diazide-5-sulfonyl chloride or a mixture of these 1,2-naphthoquinone diazide sulfonyl chlorides in a charging ratio (molar ratio) (1: 1.9.
5) to (1: 0.3), a positive photoresist composition containing a mixture of a monoester and a diester obtained by performing an esterification reaction and an alkali-soluble resin.

[0017]

[Chemical 14]

(In the formula (5), R, l, m, n and X
Represents the same meaning as in the above formula (1). )I will provide a.

The present invention will be described in detail below. The monoester body and the diester body represented by the formula (1) are prepared by adding 1,2-naphthoquinonediazide-4 (or -5) -sulfonyl chloride to the hydroxy compound of the formula (4) or the formula (5) by a known method. It can be obtained by a condensation reaction. That is, a predetermined amount of formula (4) or formula (5)
Hydroxy compounds and 1,2-naphthoquinonediazide-
A 4 (or -5) sulfonyl chloride and a solvent having no hydroxyl group such as tetrahydrofuran, dioxane, acetone, and methyl ethyl ketone are charged into a flask, and while cooling, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, A basic catalyst such as potassium hydrogen carbonate (these are preferably used as an aqueous solution), triethylamine and pyridine is slowly added dropwise for condensation, and the reaction solution is poured into water, and the precipitated product is filtered, washed with water and dried. By doing so, the target product can be obtained. The mixing ratio of the monoester and diester represented by the formula (1) can be easily changed by changing the charging ratio of the hydroxy compound and naphthoquinonediazide-sulfonyl chloride.

Specific examples of the compound represented by the formula (4) are shown below.

[0021]

[Chemical 15]

3 ', 3 "-dimethyl-phenol-phthalein, 2', 2" -dimethyl-5 ', 5 "-diisopropyl-phenol-phthalein 2', 3 ', 2", 3 "-tetramethyl-pheno -Ruphthalein, 3'-chloro-phenol-phthalein,
3 ', 5 "-dichloro-phenol-phthalein, 3',
5 "-dibromo-phenol-phthalein, 3 ', 5',
3 "-trichloro-phenol-phthalein, 4,5,6
7-tetrachloro-2 ', 2 "-dimethyl-5', 5"-
Diisopropyl-phenol-phthalein, 6-methoxy-phenol-phthalein, 6-methyl-phenol-phthalein, 3 ', 3 "-dimethoxy-phenol-phthalein,

Specific examples of the compound represented by the formula (5) are shown below.

[0024]

[Chemical 16]

3 ', 3 "-Dimethyl-sulfophthalein, 2', 2" -dimethyl-5 ', 5 "-diisopropyl-sulfophthalein, 2', 3 ', 2", 3 "-tetramethyl- Sulfophthalein, 3 ', 5 "-dichloro-
Sulfophthalein, 3 ', 5 "-dibromo-sulfophthalein, 3', 5" -dichloro-sulfophthalein,
3 ', 5', 3 "-trichloro-sulfophthalein,
4,5,6,7-Tetrachloro-2 ', 2 "-dimethyl-5', 5" -diisolopyr-sulfophthalein, 6-
Methoxy-sulfophthalein, 6-methyl-sulfophthalein, 3 ', 3 "-dimethoxy-sulfophthalein,

3 ', 3 "-dimethyl-fluorescein,
2 ', 2 "-dimethyl-5', 5" -diisopropyl-
Fluorescein, 2 ', 3', 2 ", 3" -tetramethyl-fluorescein, 3 ', 5 "-dibromo-fluorescein, 3', 5" -dichloro-fluorescein,
3 ', 5', 3 "trichloro-fluorescein, 4,
5,6,7-Tetrachlor-2 ', 2 "-dimethyl-
5 ', 5 "-diisolopyr-fluorescein, 6-methoxy-fluorescein, 6-methyl-fluorescein,
3 ', 3 "-dimethoxy-fluorescein,

4 ', 4 ", 3-trioxy-3- (1-
Sulfo-phenyl) -xanthene, 4 ', 4 ", 3-trioxy-3- (1-sulfo-6-methyl-phenyl)
-Xanthene, 4 ', 4 ", 3-trioxy-3- (1
-Sulfo-6-methoxy-phenyl) -xanthene,
3 ', 3 "-dimethyl-4', 4", 3-trioxy-
3- (1-sulfo-phenyl) -xanthene, 2 ',
2 "-dimethyl-5 ', 5"-diisopropyl-4',
4 ", 3-trioxy-3- (1-sulfo-phenyl)
-Xanthene, 2 ', 3', 2 ", 3" -tetramethyl-4 ', 4 ", 3-trioxy-3- (1-sulfo-phenyl) -xanthene, 3', 5" -dibromo-4 ' ，
4 ", 3-trioxy-3- (1-sulfo-phenyl)
-Xanthene, 3 ', 5'-dichloro-4', 4 ", 3
-Trioxy-3- (1-sulfo-phenyl) -xanthene, 4 ', 5 ", 3"-trichloro-4', 4 ", 3
-Trioxy-3- (1-sulfo-phenyl) -xanthene, 4,5,6,7-tetrachloro-2 ', 2 "-
5 ', 5 "-diisopropyl-4', 4", 3-trioxy-3- (1-sulfo-phenyl) -xanthene,

The hydroxy compound of formula (4) or formula (5) and 1,2-naphthoquinonediazide-4 (or -5)
-The charging ratio (molar ratio) with sulfonyl chloride is
(Hydroxy compound: 1,2-naphthoquinone diazide sulfonyl chloride) (1: 1.95)
(1: 0.3) is preferable. The molar ratio of 1,2-naphthoquinone diazide sulfonyl chloride charged was 1.95.
When the ratio is larger, the residual film ratio is high, but the sensitivity is lowered and a residue is liable to be generated after development. On the contrary, when the molar ratio of 1,2-naphthoquinonediazidesulfonyl chloride charged is less than 0.3, the sensitivity is increased but the residual ratio is increased. The film rate tends to decrease and the pattern tends to become thinner. Examples of the alkali-soluble resin used in the present invention include polyhydroxystyrene and its derivatives, styrene-maleic anhydride copolymer, alkali-soluble novolac resin, and the like, which show alkali-solubility and are compatible with the compound of formula (1). Any material having solubility can be used. These resins can be used alone or in combination of two or more.

The composition ratio of the alkali-soluble resin and the mixture of the monoester and diester in the present invention is
The amount of the mixture is 5 to 100 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the resin. If the ratio of the mixture is less than 5 parts by weight, the inhibitory power against the alkali developing solution and the residual film rate will decrease, and if it exceeds 100 parts by weight, the sensitivity will tend to decrease.

The positive photoresist composition of the present invention is usually used by dissolving it in a solvent. Solvents for dissolving the compound of formula (1) and the alkali-soluble resin are methyl ethyl ketone, cyclohexanone, methyl cellosolve, ethyl cellosolve, Methyl cellosolve acetate, ethyl cellosolve acetate, 1-methoxy-2-propyl-
Acetate, methyl lactate, ethyl lactate, propyl lactate, etc. can be used. Particularly, the above lactates and 1-methoxy-2-propyl-acetate, which have a strong dissolving power for the photosensitive material and the resin and have low toxicity, are useful. These solvents may be used alone or in admixture of two or more.

If necessary, the positive photoresist composition of the present invention may contain a dye, an adhesion aid, a surfactant, a storage stabilizer, an antifoaming agent and the like. The positive photoresist composition of the present invention is dissolved in the above solvent so that the solid content is 5 to 100% by weight, filtered, applied to a substrate such as a silicon wafer by a spin coater or the like, dried and passed through a predetermined mask. A good resist pattern can be obtained by exposing and developing. The exposure is performed under the condition of 50 to 300 mJ / cm ² using g-line (436 nm) or i-line (365 nm) of a high pressure mercury lamp.
After being exposed, it is developed, but as a developing solution which can be used, an aqueous solution of an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or tetramethylammonium hydroxide, trimethanolamine, triethanolamine. Examples thereof include an aqueous solution of an organic alkali.

[0032]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Synthesis Example 1 Synthesis of Photosensitive Material A Fluorescein 19.8 g (0.06 mol), 1,2-
Naphthoquinone diazide-5-sulfonyl chloride 1
6.1 g (0.06 mol) and tetrahydrofuran 200
A three-necked flask was charged with ml, and a mixed solution of 6.06 g (0.06 mol) of triethylamine and 50 ml of tetrahydrofuran was slowly added dropwise while cooling with water. After completion of the dropping, the mixture was reacted at 20 ° C. for 3 hours, the reaction solution was poured into a large amount of ion-exchanged water, the resulting precipitate was filtered off, washed with ion-exchanged water and dried to give 1,2-naphthoquinonediazide-5-sulfone of fluorescein. An acid ester was obtained. Yield 16.0g
Met. In addition, the obtained sulfonic acid ester was dissolved in tetrahydrofuran and two columns G2000H (manufactured by Tosoh Corporation) were used in a GPC system (manufactured by Shimadzu Corporation) and analyzed at a wavelength of 254 nm. As a result, the composition ratio was 54% diester. The monoester product was 46%.

Synthesis Examples 2 to 4 Synthesis of Photosensitive Materials B to D In Synthesis Example 1, except that the amounts of fluorescein, 1,2-naphthoquinonediazide-5-sulfonyl chloride charged and triethylamine were changed as shown in Table 1. Photosensitive materials B to E were obtained in the same manner as in Synthesis Example 1. The yield at that time and the analysis result by the GPC system measured in the same manner as in Synthesis Example 1 are shown in Table 1. (Photosensitive material D is for comparison test)

Synthesis Example 5 Synthesis of Photosensitive Material E 20.0 g (0.06 mol) of o-cresolphthalein, 16.1 g (0.06 mol) of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 100 ml of tetrahydrofuran. A three-necked flask was charged, and a mixed solution of 5.9 g (0.06 mol) of triethylamine and tetrahydrofuran was slowly added dropwise while cooling with water. After completion of the dropping, the mixture was reacted at 20 ° C. for 3 hours, the reaction solution was poured into a large amount of ion-exchanged water, the resulting precipitate was filtered off, washed with ion-exchanged water, and dried to give 1,2-naphthoquinonediazide of o-cresolphthalein. -5-sulfonic acid ester was obtained.
The yield was 31 g. The obtained sulfonic acid ester was dissolved in tetrahydrofuran, and two columns G2000H (manufactured by Tosoh Corporation) were used in a GPC system (manufactured by Shimadzu Corporation) and analyzed at a wavelength of 254 nm. As a result, the composition ratio was 52% diester. , Monoester body 48
%Met.

Synthesis Example 6 Synthesis of Photosensitive Material F Thymolphthalein 21.5 g (0.05 mol),
1,3-naphthoquinonediazide-5-sulfonyl chloride 13.4 g (0.05 mol) and 100 ml of tetrahydrofuran were placed in a three-necked flask, and a mixture of triethylamine 5.05 g (0.05 mol) and tetrahydrofuran was cooled with water. Drop slowly. After completion of the dropping, the reaction was allowed to proceed at 20 ° C. for 3 hours, the reaction solution was poured into a large amount of ion-exchanged water, the resulting precipitate was separated by filtration, and washed with ion-exchanged water.
It was dried to obtain 1,2-naphthoquinonediazide-5-sulfonic acid ester of thymolphthalein. Yield 28
It was g. Further, the obtained sulfonic acid ester was dissolved in tetrahydrofuran, and a column G2000H (manufactured by Tosoh Corporation) was added to a GPC system (manufactured by Shimadzu Corporation).
As a result of analysis using two of them at a wavelength of 254 nm, the composition ratio was 60% diester and 40% monoester.

Synthesis Example 7 Synthesis of Photosensitive Material G 24.6 g (0.06 mol) of p-xylenol blue, 16.1 g (0.06 mol) of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 200 ml of tetrahydrofuran were mixed. A mixed solution of 6.06 g (0.06 mol) of triethylamine and 50 ml of tetrahydrofuran was slowly added dropwise to a one-necked flask while cooling with water. After completion of the dropping, the reaction was allowed to proceed at 20 ° C. for 3 hours, the reaction solution was poured into a large amount of ion-exchanged water, the resulting precipitate was filtered off, washed with ion-exchanged water, and dried to obtain p-xylenol blue 1,2-naphthoquinonediazide. 5-sulfonic acid ester was obtained. The yield was 12 g. In addition, the obtained sulfonic acid ester was dissolved in tetrahydrofuran, and a column G2000H was added to a GPC system (manufactured by Shimadzu Corporation).
As a result of analysis using two (manufactured by Tosoh Corporation) at a wavelength of 254 nm, the composition ratio was 40% diester and 60% monoester.

Synthesis Example 8 Synthesis of Photosensitive Material H Fluorescein 19.8 g (0.06 mol), 1,2-
Naphthoquinonediazide-4-sulfonyl chloride 1
6.1 g (0.06 mol) and tetrahydrofuran 200
A three-necked flask was charged with ml, and a mixed solution of 6.06 g (0.06 mol) of triethylamine and 50 ml of tetrahydrofuran was slowly added dropwise while cooling with water. After completion of the dropping, the mixture was reacted at 20 ° C. for 3 hours, the reaction solution was poured into a large amount of ion-exchanged water, the resulting precipitate was filtered off, washed with ion-exchanged water and dried to give 1,2-naphthoquinonediazide-5-sulfone of fluorescein. An acid ester was obtained. The yield was 14 g. Further, the obtained sulfonic acid ester was dissolved in tetrahydrofuran, and two GPC system (manufactured by Shimadzu Corporation) column G2000H (manufactured by Tosoh Corporation) were used and analyzed at a wavelength of 254 nm. As a result, the composition ratio was 57% diester, It was 43% of a monoester body.

Synthesis Example 9 Synthesis of Photosensitive Material I 7.38 g (0.03 mol) of 2,3,4,4'-tetrahydroxybenzophenone, 24.17 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride (0.
(09 mol) and 150 ml of tetrahydrofuran were charged in a three-necked flask, and triethylamine 9.0 while cooling with water.
A mixture of 9 g and tetrahydrofuran is slowly added dropwise. After completion of the dropping, the reaction is allowed to proceed at 20 ° C. for 3 hours, the reaction solution is poured into a large amount of ion-exchanged water, the resulting precipitate is filtered off, washed with ion-exchanged water and dried to give 2,3,4,4′-tetrahydroxybenzophenone. 1,2-naphthoquinonediazide-5-sulfonic acid ester was obtained. The yield was 25 g. Further, the obtained sulfonic acid ester was dissolved in tetrahydrofuran and two columns G2000H (manufactured by Tosoh Corporation) were used in a GPC system (manufactured by Shimadzu Corporation) and analyzed at a wavelength of 254 nm. As a result, the composition ratio was tetraester 61. %, And the diester form was 39%. (For comparison test)

Examples 1 to 7 Photosensitive materials A to C and E obtained in Synthesis Examples 1 to 3 and 5 to 9
~ H each 2g and alkali-soluble novolac resin MER-
10g of 7969 (manufactured by Meiwa Kasei Co., Ltd .; styrene-equivalent weight average molecular weight of 12000) was dissolved in 38g of ethyl lactate and filtered using a 0.2 µm Teflon membrane filter to prepare photoresist compositions. This photoresist composition was applied onto a silicon wafer with a spinner and dried on a hot plate set at 90 ° C. for 90 seconds to obtain a resist film having a film thickness of 1.25 μm. A 500W xenon-mercury lamp was applied to this film.
The film was exposed through a UV-D35 / V-42 filter (manufactured by Toshiba Glass Co., Ltd.) through a mask on which a fine pattern was drawn (light intensity 4.5 mW / cm ² ). After exposure, 1
It was baked for 90 seconds on a hot plate set at 00 ° C, and developed with 2.38% TMAH (tetramethylammonium hydroxide) at 23 ° C for 60 seconds. The resist pattern thus obtained was observed with a scanning electron microscope to evaluate the resist. The results are shown in Table 2.

[0041] Table 1     Photosensitive material PHE NQ TEA Yield Di / mono                 g (mol) g (mol) g (mol) g       B 19.8 (0.06) 24.0 (0.09) 9.09 (0.09) 33 80/20       C 19.8 (0.06) 8.1 (0.03) 3.03 (0.03) 13 33/67       D 19.8 (0.06) 32.1 (0.12) 12.10 (0.12) 39 100/0

(Note) PHE: Fluorescein NQ: 1,2-naphthoquinonediazide-5-sulfonyl chloride TEA: triethylamine di-form / mono-form: composition ratio measured by GPC

[0043] Table 2 Example Photosensitive material Relative sensitivity Resolution Remaining film rate Pattern shape                                 (Μm) (%)   1 A 1.7 0.5 98   2 B 1.3 0.5 98   3 C 2.5 0.5 96 FIG.   4 E 1.7 0.5 98 FIG.   5 F 2.0 0.5 96 FIG.   6 G 2.0 0.75 96   7 H 1.7 0.5 98 FIG.

Comparative Example 2 g each of the photosensitive materials D and I obtained in Synthesis Examples 4 and 9 and 10 g of alkali-soluble novolac resin MER-7969
Was dissolved in 38 g of ethyl lactate and filtered through a 0.2 μm Teflon membrane filter to prepare photoresist compositions. The photoresist composition thus prepared was evaluated in the same manner as in Examples 1 to 8 and the results are shown in Table 3.

[0045] Table 3 Comparative example Photosensitive material Relative sensitivity Resolution Remaining film rate Pattern shape                                   (Μm) (%)   1 D 0.9 0.5 99 * 1   2 I 1.0 0.75 95

(Note) * 1 Residue was observed during the pattern.

In Tables 2 and 3, the sensitivities are expressed as relative sensitivities defined below, with exposure doses for reproducing 1.0 μm mask patterns. Relative sensitivity = sensitivity of Comparative Example 2 / sensitivity of each example. Therefore, the higher the relative sensitivity, the higher the sensitivity.
The residual film rate represents the percentage of the film thickness ratio of the unexposed area before and after development. The resolution is represented by the minimum resolution pattern size when exposed with an exposure amount that reproduces a mask pattern of 1.0 μm.

From the results of Comparative Example 1, phenols and 1,
It was found that when the charging ratio with 2-naphthoquinone diazide sulfonyl chloride was (1: 1.95) or more, the residue between patterns increased. Furthermore, from the results of Comparative Example 2, the relative sensitivity of the photosensitizer of the present invention to the benzophenone-based photosensitizer conventionally used is 1.5 to 2.5 times, which is extremely high.
It was found that the residual film rate and the resolution were also excellent. A cross-sectional view of a resist pattern profile in the example of the present invention is shown in FIG. 1, and a resist pattern profile of a conventional benzophenone-based resist (Comparative Example 2) is shown in FIG.

[0049]

The positive photoresist composition using the mixture of the monoester and diester of the 1,2-naphthoquinonediazide compound and the alkali-soluble resin of the present invention has extremely high sensitivity to radiation and is transferred to the substrate. Since the resist pattern has almost no film loss and the resolution is extremely excellent, it is extremely useful for manufacturing a semiconductor integrated circuit.

[Brief description of drawings]

FIG. 1 is a sectional view showing a resist pattern profile of the present invention.

FIG. 2 is a cross-sectional view showing a resist pattern profile of Comparative Example 2.

[Description of Reference Signs] In FIGS. 1 and 2, A represents a resist and B represents a silicon wafer.

Claims (5)

[Claims] 1. In the compound represented by the formula (1), R ₁ or R ₂ is a monoester of the formula (6) or the formula (7), and R ₁ and R ₂ are the formula (6) or the formula. (7) A positive photoresist composition containing a mixture with a diester of (which may be the same or different) and an alkali-soluble resin. [Chemical 2] [Chemical 3] (X in the formula (1) represents -CO- or -SO ₂ - and, R
₁ and R ₂ may be the same or different and each represents a hydrogen atom or a group of formula (6) or (7). R may be the same or different and may be a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, or a substituted Represents an optionally substituted acyl group or an optionally substituted acyloxy group. Further, l, m and n each represent an integer of 1 to 3, and the 6'carbon atom and the 6 "carbon atom of the benzene nucleus may be bonded via an oxygen atom.) 2. In the compound represented by the formula (2), R ₁ or R ₂ is a monoester of the formula (6) or the formula (7), and R ₁ and R ₂ are the formula (6). Alternatively, a positive photoresist composition containing a mixture with a diester of formula (7) (which may be the same or different) and an alkali-soluble resin: (In the formula (2), R ₁ , R ₂ , R, 1, m, n and X
Represents the same meaning as in the above formula (1). ) 3. In the compound represented by the formula (3), R ₁ or R ₂ is a monoester of the formula (6) or (7), and R ₁ and R ₂ are the formula (6). Or a positive photoresist composition containing a mixture with a diester of formula (7) (which may be the same or different) and an alkali-soluble resin: (In the formula (3), R ₁ , R ₂ , R, 1, m, n and X
Represents the same meaning as in the above formula (1). ) 4. A phenol represented by formula (4):
1,2-naphthoquinonediazide-4-sulfonyl chloride or 1,2-naphthoquinonediazide-5-sulfonyl chloride or a mixture of these 1,2-naphthoquinonediazidesulfonyl chlorides was charged at a ratio (molar ratio) (1: 1.95) to A positive photoresist composition containing a mixture of a monoester and a diester obtained by performing an esterification reaction in the range of (1: 0.3) and an alkali-soluble resin. ] (In the formula (4), R, 1, m, n and X have the same meanings as in the formula (1).) 5. A phenol represented by formula (5),
1,2-naphthoquinonediazide-4-sulfonyl chloride or 1,2-naphthoquinonediazide-5-sulfonyl chloride or a mixture of these 1,2-naphthoquinonediazidesulfonyl chlorides was charged at a ratio (molar ratio) (1: 1.95) to A positive photoresist composition containing a mixture of a monoester and a diester obtained by performing an esterification reaction in the range of (1: 0.3) and an alkali-soluble resin. ] (In the formula (5), R, 1, m, n and X have the same meanings as in the formula (1).)