JP2000258901A - Radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the radiation sensitive resin composition suitable for a positive resist superior in developability. SOLUTION: The radiation sensitive resin composition comprises (A) an alkali-soluble phenol compound obtained by condensation of the phenol compounds comprising at least 5 mol% p-cresol, and m-cresol and 2,3-xylenol, and aldehyde in the presence of an acid catalyst, and (B) quinonediazide sulfonate ester, and (C) 5-40 pts.wt. of a phenol compound having a molecular weight of 100-1,000 per 100 pts.wt. of the alkali-soluble phenol resin of the above (A) component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a radiation-sensitive resin composition containing an alkali-soluble resin. More specifically, high integration sensitive to various types of radiation such as ultraviolet rays such as g-rays and i-rays, far ultraviolet rays such as KrF excimer lasers, X-rays such as synchrotron radiation, and charged particle beams such as electron beams, particularly ultraviolet rays and far ultraviolet rays. The present invention relates to a radiation-sensitive resin composition suitable as a circuit-forming resist.

[0002]

2. Description of the Related Art Positive resists are widely used in the manufacture of integrated circuits, but the required performance has been diversified with the recent increase in the degree of integration of integrated circuits. For example, development conditions also vary in the manufacturing process of each device. In particular, it is expected that the developing solution leakage time during development will increase as the wafer diameter increases. Therefore, the time required for a fresh developer to contact the surface of the resist is prolonged, and a positive resist excellent in process margin that can be applied to such severe development conditions is required.
In general, when the development conditions are severe, especially in the case of a novolak / quinonediazide-based positive resist composition, the formation of the surface insolubilized layer of the resist is promoted, the resolution is lowered, and the scum which does not dissolve in the alkaline developer (development residue) Formation is promoted.

[0003]

Accordingly, an object of the present invention is to provide a radiation-sensitive resin composition suitable as a positive resist excellent in developability.

[0004]

According to the present invention, the object is to provide (A) p-cresol at least 5 mol%, m
-An alkali-soluble phenol resin obtained by condensing a phenol compound comprising cresol and 2,3-xylenol with an aldehyde in the presence of an acidic catalyst, (B) a quinonediazidesulfonic acid ester compound, and
(C) The alkali-soluble phenolic resin 1 of the component (A)
5 to 40 parts by weight per 100 parts by weight, molecular weight 100 to 10
This is achieved by a radiation-sensitive resin composition containing a phenol compound of No. 00.

Hereinafter, the present invention will be described in detail. (A) Alkali-Soluble Resin The amount of p-cresol used in the production of the alkali-soluble resin (hereinafter referred to as “resin (A)”) used as the component (A) in the present invention is 5 mol% based on the whole phenol compound. At least 10 mol% and at least 30 mol%
A range of at most mol% is preferred. The amount of m-cresol is
5 mol% or more and 60 mol% in the whole phenol compound
The following is preferable, and especially the range of 10 mol% or more and 40 mol% or less is preferable. The amount of 2,3-xylenol is preferably 20 mol% or more and 80 mol% or less, particularly preferably 30 mol% or more and 70 mol% or less in the whole phenol compound.

Examples of the aldehyde to be condensed with the phenol compound include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde,
Examples thereof include m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde, and isophthalaldehyde. Among these, formaldehyde and o-hydroxybenzaldehyde can be particularly preferably used. These aldehydes may be used alone or
More than one species can be used in combination. The amount of the aldehyde used is 0.1 mol per 1 mol of the phenol compound.
It is preferably from 4 to 2 mol, more preferably from 0.6 to 1.5 mol.

[0007] An acidic catalyst is used for the condensation reaction between the phenol compound and the aldehyde. Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid,
Examples thereof include methanesulfonic acid and p-toluenesulfonic acid, and among them, sulfuric acid, oxalic acid and p-toluenesulfonic acid are preferred. The use amount of these acidic catalysts is usually 1 × 10
^{−5 to} 5 × 10 ⁻¹ mol.

In the condensation reaction, water is usually used as a reaction medium. However, when the phenol compound used in the reaction does not dissolve in an aqueous aldehyde solution and becomes a heterogeneous system from the beginning of the reaction, a hydrophilic medium is used as the reaction medium. It is preferable to use a neutral solvent. Examples of such a hydrophilic solvent include alcohols such as methanol, ethanol, propanol, butanol and propylene glycol monomethyl ether; cyclic ethers such as tetrahydrofuran and dioxane; and ketones such as ethyl methyl ketone, methyl isobutyl ketone and 2-heptanone. And the like. The amount of the reaction medium is usually 20 to 1,000 parts by weight per 100 parts by weight of the reaction raw material. The temperature of the condensation reaction can be appropriately adjusted depending on the reactivity of the raw materials, but is usually from 10 to 200 ° C.

As a reaction method, a method in which a phenol compound, an aldehyde, an acidic catalyst and the like are collectively charged into a reaction vessel, and an acidic catalyst is previously present in the reaction system, and the phenol compound, the aldehyde and the like are added thereto as the reaction proceeds. The addition method or the like can be appropriately adopted.

After the completion of the condensation reaction, for example, in order to remove unreacted raw materials, acidic catalyst, reaction medium and the like existing in the system,
The reaction temperature is increased to 130 ° C. to 230 ° C., and volatile components are removed under reduced pressure, so that the novolak resin can be recovered.

[0011] The weight average molecular weight in terms of polystyrene (hereinafter abbreviated as Mw) measured by gel permeation chromatography (detector: differential refractometer) is determined by the workability and the composition when the obtained composition is applied to a substrate. In terms of developability, sensitivity and heat resistance when using the product as a resist,
It is preferable that 2,000 ≦ Mw ≦ 20,000,
It is particularly preferred that 3,000 ≦ Mw ≦ 15,000.

The polystyrene equivalent molecular weight is 5,000.
The peak area ratio of 0 or more is defined as S1 (%), 1,000 or more,
The peak area ratio of less than 000 is determined by S2 (%) and
Assuming that the peak area ratio less than 0 is S3 (%), 30 ≦ S
It is preferable that 1 ≦ 80, 20 ≦ S2 ≦ 60 and 0 ≦ S3 ≦ 10.

In order to obtain a high-molecular-weight alkali-soluble resin having a Mw of 2,000 or more, the resin (A) obtained by the above-mentioned synthesis method or the like can be obtained by, for example, using ethylene glycol monomethyl ether acetate, 3-methoxypropione. After dissolving in a good solvent such as methyl acid, methyl isobutyl ketone, dioxane, methanol and ethyl acetate, the resulting solution is mixed with a poor solvent such as water, n-hexane and n-heptane to precipitate a resin solution layer. Then, the precipitated resin solution layer may be separated and collected.

(B) Quinonediazidesulfonic acid ester
Compound The quinonediazidesulfonic acid ester compound used in the present invention includes 1,2-benzoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound,
Naphthoquinonediazide-4-sulfonic acid ester, 1,
Examples thereof include 2-naphthoquinonediazide-5-sulfonic acid ester and 1,2-naphthoquinonediazide-6-sulfonic acid ester. Particularly, 1,2-naphthoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide- 5-sulfonic acid esters are preferred.

The quinonediazidesulfonic acid ester compound can be obtained, for example, by reacting a polyhydroxy compound with quinonediazidosulfonyl chloride corresponding to the required quinonediazidesulfonic acid ester in the presence of a basic catalyst. Usually, the average ratio of esterification of all the hydroxyl groups of the polyhydroxy compound (hereinafter referred to as average esterification ratio) is 20% to 100%, preferably 40% to 95%. If the average esterification rate is too low, it is difficult to form a pattern, and if it is too high, sensitivity may be reduced. Here, the polyhydroxy compound used is not particularly limited, but specific examples include compounds represented by the following formulas (1-1) to (1-8).

[0016]

Embedded image (1-1) [wherein, X _{1 to} X ₁₅ are the same or different and each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a 5 to 7 carbon atoms. It is a cycloalkyl group or a hydroxyl group. However, at least one of the groups X _{1 to} X ₅ , X _{6 to} X ₁₀ and X _{11 to} X ₁₅ is a hydroxyl group. Y ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[0017]

Embedded image(1-2) [wherein, X₁₆~ X₃₀Is the X₁~ X_FifteenSame as
is there. Where X₁₆~ X ₂₀, X₂₁~ X₂₅And X
₂₆~ X₃₀At least one is a hydroxyl group in each group of
is there. Also, Y₂~ Y₄Are the same or different
Or an alkyl group having 1 to 4 carbon atoms. ]

[0018]

Embedded image(1-3) [wherein, X₃₁~ X₄₄Is the X₁~ X_FifteenSame as
is there. Where X₃₁~ X ₄₄At least one in the group
One is a hydroxyl group. Also, Y₅~ Y₈Are the same or different
With a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
is there. ]

[0019]

Embedded image(1-4) [wherein, X₄₅~ X₅₈Is the X₁~ X_FifteenSame as
is there. Where X₄₅~ X ₄₉, X₅₀~ X₅₃, X₅₄
~ X₅₇And X₅₈~ X₆₂At least in each group
One is a hydroxyl group. Also, Y₉~ Y₁₄Are the same
Or a hydrogen atom or an alkyl having 1 to 4 carbon atoms
Group. ]

[0020]

Embedded image(1-5) [wherein, X₆₃~ X₈₄Is the X₁~ X_FifteenSame as
is there. Where X₆₃~ X ₆₇, X₆₈~ X₇₁, X₇₆~
X₇₉And X₈₀~ X₈₄At least one in each group of
It is a hydroxyl group. Also, Y₁₅~ Y_{twenty two}Are the same or different
And is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
You. ]

[0021]

Embedded image (1-6) wherein X _{85 to} X ₁₀₈ are the same as X _{1 to} X ₁₅ described above. _{However, X 85 ~X 8 9, X} 90 ~X 94, X 95 ~X 98,
At least one keep each group of X ₉₉ to X ₁₀₃ and X ₁₀₄ to X ₁₀₈ is a hydroxyl group. Y ₂₃ and Y ₂₄ are the same or different and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[0022]

Embedded image (1-7) wherein X _{109 to} X ₁₂₂ are the same as X _{1 to} X ₁₅ described above. However, at least one of the groups X _{109 to} X ₁₁₂ and X _{113 to} X ₁₁₇ is a hydroxyl group. Also, Y _{25 to} Y
₂₆ is the same or different and has 1 hydrogen atom or 1 carbon atom
To 4 alkyl groups. ]

[0023]

Embedded image (1-8) wherein X _{123 to} X ₁₃₁ are the same as X _{1 to} X ₁₅ described above. However, at least one of the groups X _{123 to} X ₁₂₆ and X _{127 to} X ₁₃₁ is a hydroxyl group. Also, Y _{27 to} Y
₂₈ are the same or different and each is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or Y _{27 to} Y ₂₈ are bonded together to form a carbon atom having 6 or less carbon atoms together with the carbon atoms to which they are bonded. Form a cycloalkane ring. Furthermore, Y _{29 to} Y ₃₀ are the same or different and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or Y _{29 to} Y ₃₀
Are bonded together to form a cycloalkane ring having 6 or less carbon atoms together with the carbon atoms to which they are bonded. ]

In the above formulas (1-1) to (1-8), examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isbutyl and tert-butyl. Groups. 1 carbon atom
Examples of the alkoxy groups 4 to 4 include methoxy, ethoxy, propoxy and butoxy groups. 5 carbon atoms
Examples of the cycloalkyl group 7 include a cyclohexyl group. These quinonediazidesulfonic acid ester compounds can be used alone or in combination of two or more.

In the composition of the present invention, the quinonediazidesulfonic acid ester compound (B) is
0 to 5 parts by weight, usually 5 to 50 parts by weight, especially 5 to
It is preferred to use 40 parts by weight. at the same time,
The ratio of the 1,2-quinonediazidosulfonyl residue contained in the component (B) to the total solid content of the composition of the present invention is as follows:
Preferably 5 to 50% by weight, more preferably 10 to 30%
% By weight.

(C) Phenol compound A molecular weight of 100 to 1 used as the component (C) in the present invention.
Phenol compound (hereinafter, referred to as phenol compound (C)) serves as a dissolution accelerator for resin (A), and for example, has the following general formula (2-1) to
The compound represented by (2-6) is mentioned.

[0027]

Embedded image (2-1) wherein Z ₁ is independently a hydrogen atom or a methyl group. Z _{2 to} Z ₁₁ are each independently a hydrogen atom, a methyl group or a hydroxyl group. However, at least one of Z _{2 to} Z ₁₁ is a hydroxyl group. ]

[0028]

Embedded image (2-2) wherein Z ₁₂ is independently a hydrogen atom or a methyl group. Z _{13 to} Z _{26 each} independently represent a hydrogen atom, a methyl group or a hydroxyl group. However, at least one of Z _{18 to} Z ₂₁ is a hydroxyl group. ]

[0029]

Embedded image (2-3) wherein Z ₂₇ is a hydrogen atom or a methyl group. Z ₂₈
To Z ₄₂ independently represent a hydrogen atom, a methyl group or a hydroxyl group. However, at least one of Z _{28 to} Z ₄₂ is a hydroxyl group. ]

[0030]

Embedded image (2-4) wherein Z _{43 to} Z ₅₂ are independently a hydrogen atom, a methyl group or a hydroxyl group, provided that at least one of them is a hydroxyl group. ]

[0031]

Embedded image (2-5) wherein Z _{53 to} Z ₆₇ are each independently a hydrogen atom, a methyl group or a hydroxyl group, provided that at least one of them is a hydroxyl group. ]

[0032]

Embedded image (2-6) wherein Z _{68 to} Z _{91 each} independently represent a hydrogen atom, a methyl group or a hydroxyl group, provided that at least one of them is a hydroxyl group. Among the compounds represented by the general formulas (2-1) to (2-6), the compounds represented by (2-2) and (2-4) are preferable.

Preferred specific examples of the phenol compound (C) include, for example, the following compounds (3-1) to (3-
5).

[0034]

Embedded image (3-1)

[0035]

Embedded image (3-2)

[0036]

Embedded image (3-3)

[0037]

Embedded image (3-4)

[0038]

Embedded image (3-5) These phenol compounds (C) can be used alone or in combination of two or more.
It is preferable to contain 5 to 40 parts by weight per part by weight,
In particular, it is preferable to contain 10 to 40 parts by weight.

Other Components Various optional components can be added to the composition of the present invention as needed. Surfactant: A surfactant is used to improve the coating properties and developability of the composition. Examples of such surfactants include polyoxyethylene lauryl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, Megafax F171, F1
72, F173, F471, R-07, R-08 (trade name, manufactured by Dainippon Ink), Florade FC430, FC
431 (trade name, manufactured by Sumitomo 3M Limited), Asahigard AG710, Surflon S-382, SC-101, S
C-102, SC-103, SC-104, SC-10
5, SC-106 (trade name, manufactured by Asahi Glass Co., Ltd.), KP341
(Trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 7
5, No. 95 (trade name, manufactured by Kyoeisha Yushi Kagaku Kogyo),
NBX-7, NBX-8, NBX-15 (trade name, manufactured by Neos) and the like. The amount of these surfactants is not more than 2 parts by weight per 100 parts by weight of the solid content of the composition.

Further, the composition of the present invention may contain a dye or a pigment in order to visualize the latent image of the radiation-irradiated portion of the resist and reduce the influence of halation upon radiation irradiation. In order to improve the adhesiveness, an adhesion aid may be added. Further, a storage stabilizer, an antifoaming agent and the like can be added as required.

Solvent: The composition of the present invention is prepared by adding the solid components such as component (A), component (B) and component (C) to a solvent such that the solid component concentration becomes, for example, 20 to 40% by weight. It is prepared by dissolving and filtering through a filter having a pore size of about 0.2 μm. Examples of the solvent used herein include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, and propylene glycol. Monopropyl ether acetate, toluene, xylene, methyl ethyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3- Methyl methyl butanoate, methyl 3-methoxypropionate, 3-ethoxy Shipuropion ethyl 3-methoxy propionate,
Ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate and the like can be used in combination. Furthermore, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone , Isophorone, caproic acid, caprylic acid, 1-octanol,
1-nonanol, benzyl alcohol, benzyl acetate,
High-boiling solvents such as ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate can also be added.

Among them, preferred solvents include, for example, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, 2-heptanone, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate. And the like. These solvents are
They are used alone or in combination of two or more.

Use The composition of the present invention is useful as a resist. The method of forming a resist film using this composition, for example,
The composition is coated on a substrate to form a coating film, the resulting coating film is dried to form a resist film, and the surface of the obtained resist film is selectively exposed to radiation to form a latent image. Forming
It includes various steps of developing the formed latent image. More specifically, the composition of the present invention usually prepared as a solution is applied to a silicon wafer or a wafer coated with aluminum or the like by spin coating, casting coating, roll coating, or the like. Next, a resist film was formed by pre-baking the resist film, and the resist film was irradiated with radiation using, for example, a mask so as to form a desired resist pattern, and then patterned by developing with a developer. A resist film is formed.

The radiation used at this time is g-ray,
Ultraviolet rays such as i-rays are preferably used, but various radiations such as far ultraviolet rays such as excimer laser, X-rays such as synchrotron radiation, and charged particle beams such as electron beams can also be used.

Further, the composition of the present invention forms a resist film, and after prebaking and irradiation,
The effect of the present invention can be further improved by performing an operation of heating at 140 ° C. (hereinafter, referred to as “post-bake”) and then performing development.

Examples of the developing solution used for the resist film include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate,
Aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, , 8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonane, etc., at a concentration of, for example, 1 to 10% by weight. An alkaline aqueous solution dissolved in water is used.
Further, a suitable amount of a water-soluble organic solvent, for example, an alcohol such as methanol or ethanol or a surfactant may be added to the developer. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

[0047]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited by these examples. <Synthesis of Resin (A)> In the following synthesis examples, Mw of the obtained resin was determined by using a GPC column (G2000H manufactured by Tosoh Corporation).
XL: 2 pcs, G3000HXL: 1 pcs, G4000HXL: 1
Using gel permeation chromatography (detector: differential refractometer) using monodisperse polystyrene as a standard under the analysis conditions of flow rate: 1.0 ml / min, elution solvent: tetrahydrofuran, column temperature: 40 ° C. It was measured.
For S1, S2 and S3, retention times corresponding to Mw of 1,000 and 5,000 were determined from a calibration curve prepared using monodisperse polystyrene, and Mw was determined.
The peak areas of the fractions of 5,000 or more, the peak areas of the fractions of Mw 1,000 or more and less than 5,000, and Mw 1,000
The peak areas of fractions less than 0 were measured, and the respective area ratios were determined.

Synthesis Example 1 In a 1 L autoclave, 32.4 g of m-cresol was added.
(0.3 mol), p-cresol 10.8 g (0.1
Mol), 73.3 g of 2,3-dimethylphenol
(0.6 mol), 37% by weight aqueous formaldehyde solution
77.1 g (formaldehyde: 0.95 mol), oxalic acid dihydrate (9.5 g, 0.05 mol) and propylene glycol monomethyl ether (291 g) were charged, and the mixture was stirred for 8 hours while maintaining the internal temperature at 130 ° C. Condensation was performed. 30% by weight of this resin in ethyl acetate
And then washed with water until the ethyl acetate solution becomes neutral. Then, 1.2 times the weight of methanol and 1.0 times the amount of water were added, and the mixture was stirred for 30 minutes and left to stand for 1 hour. Was placed. The supernatant of the precipitated resin layer was removed by decantation, ethyl 2-hydroxypropionate was added, and the remaining ethyl acetate, methanol, water and propylene glycol monomethyl ether were distilled off under reduced pressure under heating to give 2- (resin (A)). An ethyl hydroxypropionate solution was obtained. Mw of this novolak resin was 8,800. This resin is abbreviated as (A1) below.

Synthesis Examples 2 and 3 The same operations as in Synthesis Example 1 were carried out except that the phenols, catalysts and aldehydes shown in Table 1 were used in Synthesis Examples 2 and 3, respectively. ) And resin (A3). Table 1 shows the results.

[0050]

[Table 1]

<Synthesis of quinonediazide compound (B)> Synthesis Example 4 In a flask equipped with a stirrer, a dropping funnel and a thermometer, 42.4 g (0.1
Mol), 67.1 g (0.25 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 547 g of dioxane were charged and dissolved with stirring. Then, the flask was immersed in a water bath controlled at 30 ° C., and when the internal temperature became constant at 30 ° C., 28.2 (0.28 mol) of triethylamine was added to the solution at an internal temperature of 35 ° C.
The solution was added using a dropping funnel so that the temperature did not exceed ℃, and the reaction was carried out at the same temperature for 2 hours. Thereafter, the precipitated triethylamine hydrochloride was removed by filtration, and the filtrate was poured into a large amount of a dilute aqueous hydrochloric acid solution to precipitate a reaction product.Then, the precipitate was filtered, collected, and dried at 40 ° C. in a vacuum dryer overnight. As a result, a quinonediazide compound (B1) was obtained.

[0052]

Embedded image

Synthesis Example 5 39.2 g (0.1 mol) of the compound represented by Formula 2;
1,2-naphthoquinonediazide-5-sulfonic acid chloride 40.2 g (0.15 mol), dioxane 476 g
And triethylamine 17.2 g (0.17 mol)
Quinonediazide compound (B2) was obtained in the same manner as in Synthesis Example 4 except that was charged.

[0054]

Embedded image

Synthesis Example 6 24.8 g (0.05 mol) of the compound represented by Formula 3;
33.5 g (0.125 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride, dioxane 35
Except that 0 g and 14.1 g (0.14 mol) of triethylamine were charged, the same operation as in Synthesis Example 4 was carried out.
A quinonediazide compound (B3) was obtained.

[0056]

Embedded image

Synthesis Example 7 36.4 g (0.1 mol) of the compound represented by Formula 4;
80.5 g (0.3 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 701 g of dioxane
And 33.3 g (0.33 mol) of triethylamine
Quinonediazide compound (B4) was obtained in the same manner as in Synthesis Example 4 except that was charged.

[0058]

Embedded image

Examples 1 to 6 The resin (A), the quinonediazide compound, the dissolution promoter and the solvent were mixed with the composition shown in Table 2 (parts are parts by weight) to obtain a uniform solution. The solution was filtered through a membrane filter having a pore size of 0.2 μm to prepare a solution of the composition. The obtained solution was applied on a silicon wafer having a silicon oxide film using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to obtain a thickness of 0.1 mm.
An 86 μm resist film was formed. Then, through a reticle, NSR-2205i12D manufactured by Nikon Corporation
Wavelength 36 with reduction projection exposure machine (lens numerical aperture = 0.63)
Exposure using 5 nm (i-line), 1 mm on hot plate
It was post-baked at 10 ° C. for 1 minute, developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide, rinsed with ultrapure water, and dried to form a resist pattern. Here, out of the development time of 60 seconds, the leakage time of the developer was changed to 3 seconds, 6 seconds, and 10 seconds. The obtained resist pattern was examined, and the properties of the composition of each example as a resist pattern were evaluated by the following methods. Table 3 shows the results. Characteristic evaluation of the obtained resist pattern
It carried out by the following method.

[0060] developability: forming a resist film of the composition,
The degree of scum after pattern formation was examined using a scanning electron microscope. When the developer bleeding time was varied, the case where the resist film surface was clean and no scum was observed was evaluated as good (○), and the case where the film surface was rough or scum was observed was evaluated as poor (×). did.

Resolution : 0.35 μm line and
The minimum dimension of the line and space pattern separated without reducing the film thickness was measured by a scanning electron microscope at the exposure amount (appropriate exposure amount) when the space pattern was resolved one-to-one.

Focus tolerance : Using a scanning electron microscope, the pattern size to be resolved is
The deviation of the focus within ± 10% of the mask design dimension was defined as the focus range and used as an evaluation index.
A large focus range means that it has good focus tolerance.

Exposure margin : The appropriate exposure amount (Eop) is set to 0.
A value obtained by dividing the exposure amount (Ec) at which the 35 μm line and space pattern starts to be resolved is defined as an exposure margin. A large value means that a good exposure margin is provided.

Heat resistance : The wafer on which the resist pattern was formed was heated on a hot plate for 2 minutes, and was heated to 2.0 μm
The temperature at which the line and space began thermal deformation was measured.

Comparative Example 1 In Comparative Example 1, a composition solution was prepared in the same manner as in Example 1 except that the resin (A3) shown in Table 1 was used instead of the resin (A). A resist pattern was formed on the substrate, and characteristics of the obtained resist pattern were examined in the same manner as in the example. Table 3 shows the results.

[0066]

[Table 2]

Dissolution promoter C1:

[0068]

Embedded image C2:

[0069]

Embedded image C3:

[0070]

Embedded image C4:

[0071]

Embedded image C5:

[0072]

Embedded image C6:

[0073]

Embedded image Solvent D1: 2-Heptanone D2: Ethyl 3-ethoxypropionate

[0074]

[Table 3]

[0075]

The radiation-sensitive resin composition of the present invention is particularly excellent in developability when used as a positive resist. Furthermore, it has excellent characteristics of resolution, heat resistance, pattern shape, exposure margin and focus tolerance, and these characteristics are exhibited in a well-balanced manner. Further, the generation of scum is effectively suppressed, and the sensitivity is good. Therefore, this composition can be suitably used as a resist for producing a highly integrated circuit.

Continuation of the front page (72) Inventor Shinichiro Iwanaga 2-11-24 Tsukiji, Chuo-ku, Tokyo FSR term in JSR Co., Ltd. (reference) 2H025 AA04 AB16 AC01 AC04 AC05 AC06 AC08 AD03 BE01 CB28 CB29 CB52 CB55 CB56 CC20 FA17

Claims (3)

[Claims] (A) an alkali-soluble phenol resin obtained by condensing a phenol compound comprising at least 5 mol% of p-cresol, m-cresol and 2,3-xylenol with an aldehyde in the presence of an acidic catalyst;
(B) a quinonediazidesulfonic acid ester compound, and (C) a molecular weight of 100 from 5 to 40 parts by weight per 100 parts by weight of the alkali-soluble phenol resin of the component (A).
Radiation-sensitive resin compositions containing from 1000 to 1000 phenolic compounds. 2. The composition according to claim 1, wherein the phenol compound of the component (C) is at least one selected from phenol compounds represented by the following general formulas (2-1) to (2-5). Embedded image (2-1) wherein Z ₁ is independently a hydrogen atom or a methyl group. Z _{2 to} Z ₁₁ are each independently a hydrogen atom, a methyl group or a hydroxyl group. However, at least one of Z _{2 to} Z ₁₁ is a hydroxyl group. [Chemical formula 2] (2-2) wherein Z ₁₂ is independently a hydrogen atom or a methyl group. Z _{13 to} Z _{26 each} independently represent a hydrogen atom, a methyl group or a hydroxyl group. However, at least one of Z _{13 to} Z ₂₁ is a hydroxyl group. [Chemical formula 3] (2-3) wherein Z ₂₇ is a hydrogen atom or a methyl group. Z ₂₈
To Z ₃₂ are independently a hydrogen atom or a methyl group, Z ₃₃
To Z ₄₂ independently represent a hydrogen atom, a methyl group or a hydroxyl group. However, at least one of Z _{33 to} Z ₄₂ is a hydroxyl group. [Formula 4] (2-4) wherein Z _{43 to} Z ₅₂ are independently a hydrogen atom, a methyl group or a hydroxyl group, provided that at least one of them is a hydroxyl group. [Chemical formula 5] (2-5) wherein Z _{68 to} Z _{91 each} independently represent a hydrogen atom, a methyl group or a hydroxyl group, provided that at least one of them is a hydroxyl group. ] 3. The alkali-soluble novolak resin has a weight average molecular weight in terms of polystyrene of 3,000 to 15,000 as measured by gel permeation chromatography (detector: differential refractometer), and is in terms of polystyrene. The area ratio of peaks having a molecular weight of 5,000 or more is expressed by S
Assuming that the area ratio of a peak of 1 (%), 1,000 or more and less than 5,000 is S2 (%), and the area ratio of a peak of less than 1,000 is S3 (%), 30 ≦ S1 ≦ 80, 20 ≦ S
3. The composition according to claim 1, wherein 2 ≦ 60 and 0 ≦ S3 ≦ 10.