JPH05289340A - Radiosensitive resin composition - Google Patents

Abstract

PURPOSE:To attain excellent development property, pattern shape and resolution and to be appropriately used even at the time of irradiating perticularly with radioactive ray of wavelength shorter than that of far ultraviolet rays. CONSTITUTION:The negative radiosensitive resin composition consists of (1) an alkali-soluble resin, (2) a radiosensitive acid forming agent, (3) a compound having a property to control alkali solubility of the alkali-soluble resin (1) and manifesting a property to lower or lose the controlling effect of alkali solubility of the alkali-soluble resin (1) by the decomposition in the presence of an acid or a property to accelerate the alkali solubility of the alkali soluble resin (1) and (4) a compound having nitrogen-contained basic group and acidic group in the molecule or the negative radiosensitive resin composition consists of (1) the alkali soluble resin, (2) the radiosensitive acid forming agent, (3) a compound to cross-link the alkali-soluble resin in the presence of an acid and (4) the compound having nitrogen-contained basic group and acidic group in the molecule.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a radiation-sensitive resin composition. More specifically, the present invention relates to a radiation-sensitive resin composition suitable as a resist useful for fine processing using radiation such as deep ultraviolet rays such as excimer laser, X-ray such as synchrotron radiation, and charged particle beam such as electron beam.

[0002]

2. Description of the Related Art In the field of microfabrication represented by the manufacture of integrated circuit devices, in recent years, in order to obtain a higher degree of integration, development of a lithography process which enables microfabrication on the order of sub-half micron has been advanced. There is.

Typical conventional resists used in the lithographic process include a negative resist using a cyclized rubber and a bisazide sensitizer and a positive resist using a novolak resin and a quinonediazide sensitizer. However, both resists are reaching the performance limit, and are extremely difficult to use in the sub-half micron order.

That is, in the above negative type resist, fine patterns come into contact with each other due to swelling during development, resulting in damage. Further, in the above positive type resist,
For example, when irradiated with far ultraviolet rays, the light absorption is too strong and the cross-sectional shape of the pattern becomes a triangle. Moreover, when irradiated with high energy radiation such as X-rays and charged particle beams, The resist is hardened to change to a negative type, and it is difficult to obtain a fine pattern suitable for a lithography process. In order to improve these points, a patterning material containing a polymer having a silyl group usable for various radiation sources has been developed (Japanese Patent Laid-Open No. 60-52845).
(See the official gazette).

[0005]

An object of the present invention is to provide a novel radiation sensitive resin composition. Another object of the present invention is that it does not swell with a developing solution and is excellent in developability, pattern shape, focus acceptability, heat resistance, adhesiveness, lithographic process stability, etc., and it is suitable for various radiation sources with high resolution and high sensitivity. It is to provide a radiation-sensitive resin composition suitable as a resist that can be used. Other objects of the present invention will be apparent from the following description.

[0006]

According to the present invention, the above objects and advantages of the present invention are as follows: (1) an alkali-soluble resin (hereinafter referred to as "resin (A)"); Radioactive acid forming agent (hereinafter referred to as "acid forming agent"), (3)
(1) the property of controlling the alkali solubility of the alkali-soluble resin, and being decomposed in the presence of an acid to reduce or eliminate the alkali-solubility controlling effect of the alkali-soluble resin of (1), or (1 (4) A compound that expresses the property of promoting alkali solubility of the alkali-soluble resin (hereinafter referred to as “dissolution control agent”), and (4) a compound having a nitrogen-containing basic group and an acidic group in the molecule. Positive-type radiation-sensitive resin composition characterized by (hereinafter,
"First invention").

According to the present invention, secondly, the above objects and advantages of the present invention include (1) a substituted methyl group, a 1-substituted ethyl group, a germyl group, an alkoxycarbonyl group, an acyl group and a silyl group. An alkali-insoluble or sparingly-soluble resin having at least one selected acid-dissociable group, which is alkali-soluble when the above group is acid-dissociated (hereinafter referred to as "resin (B)"), (2) acid Achieved with a positive-type radiation-sensitive resin composition (hereinafter referred to as "second invention"), which comprises a forming agent and (3) a compound having a nitrogen-containing basic group and an acidic group in the molecule. To be done.

Furthermore, according to the present invention, thirdly, the above objects and advantages of the present invention are as follows: (1) resin (A), (2) acid former, (3) in the presence of acid (1) Negative radiation-sensitive compound containing a compound (hereinafter, referred to as a "crosslinking agent") that crosslinks the resin (A), and (4) a compound having a nitrogen-containing basic group and an acidic group in the molecule. This is achieved by a resin composition (hereinafter referred to as "third invention").

The composition of the present invention will be described below.

Resin (A) Resin (A) used in the first and third inventions
Is not particularly limited as long as it has a property of being soluble in an alkali developing solution. Therefore, a resin having a functional group having an affinity with an alkaline developer, for example, an acidic functional group such as a phenolic hydroxyl group or a carboxyl group may be used. As a suitable resin (A), for example, the following formula (1)

[0011]

[Chemical 1]

A repeating unit represented by the following formula (2)

[0013]

[Chemical 2]

A repeating unit represented by the following formula (3)

[0015]

[Chemical 3]

The repeating unit represented by and the following formula (4)

[0017]

[Chemical 4]

A resin containing at least one repeating unit of the repeating units represented by

The resin (A) in the present invention has the formula (1),
It may be composed of only the repeating unit represented by the formula (2), the formula (3) or the formula (4), or may have other repeating units. Examples of the other repeating unit herein include maleic anhydride, fumaronitrile, acrylamide, acrylonitrile, vinylpyridine, vinylpyrrolidone, vinylimidazole, a repeating unit in which a double bond of a monomer having a double bond such as vinylaniline is cleaved. Can be mentioned.

The content of the repeating unit represented by the formula (1), the formula (2), the formula (3) and the formula (4) in the resin (A) of the present invention is generally determined by the other repeating units contained. However, it is usually 15 mol% or more, preferably 20 mol% or more. The molecular weight of the resin (A) of the present invention is determined by gel permeation chromatography (GP
The polystyrene reduced weight average molecular weight (hereinafter referred to as “Mw”) measured in C) is preferably 1,000 to 15
000, particularly preferably 3,000 to 100,000
Is.

As the method for producing the resin (A) of the present invention, it can be obtained, for example, by polymerizing a corresponding vinyl monomer, or by polycondensing phenols and aldehydes. Among these resins (A), the resin containing the repeating unit represented by the formula (1) or (2) has a hydrogenation rate of 70% or less, preferably 50% or less, more preferably 40% or less. It can also be used as a hydrogenated product.

Resin (B) The resin (B) used in the second invention is a methyl group or 1-substituted ethyl group in which a hydrogen atom such as a phenolic hydroxyl group or a carboxyl group of the acidic functional group of the resin (A) is substituted. Group, a germyl group, an alkoxycarbonyl group and an acyl group, at least one acid dissociable group (hereinafter,
It is an alkali insoluble or sparingly soluble resin substituted with “substituent B”). Here, the acid dissociable group refers to a group capable of dissociating in the presence of an acid.

Specific examples of the substituent B include a methoxymethyl group, a methylthiomethyl group, a methoxyethoxymethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiofuranyl group, a tetrahydrothiopyranyl group and a benzyloxymethyl group. , Phenacyl group, bromophenacyl group, methoxyphenacyl group, α-methylphenacyl group, cyclopropylmethyl group, cyclohexyl group, cyclopentyl group, benzyl group, triphenylmethyl group, diphenylmethyl group, bromobenzyl group, nitrobenzyl group, Substituted methyl group such as methoxybenzyl group and piperonyl group; 1-substituted ethyl group such as 1-methoxyethyl group, 1-ethoxyethyl group, isopropyl group, t-butyl group, and 1,1-dimethylpropyl group; trimethylgermyl Group, triethyl Mill group, t- butyl-dimethyl germyl group, an isopropyl dimethyl germyl group, a germyl group such as phenyl dimethyl germyl group; a methoxycarbonyl group, an ethoxycarbonyl group, an alkoxycarbonyl group such as t- butoxycarbonyl group;

Acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, lauriloyl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, succinyl group, glutaryl group. , Adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoyl group, acryloyl group, propioloyl group, methacryl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, camphoroyl group, benzoyl group, phthaloyl group, Isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group,
Acyl groups such as hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group, isonicotinoyl group, p-toluenesulfonyl group and mesyl group; and trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group Examples thereof include silyl groups such as groups, isopropylsilyl groups, and phenyldimethylsilyl groups.

Of these, a trimethylsilyl group, a t-butyl group, a benzyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, a tetrahydrothiofuranyl group, a tetrahydrothiopyranyl group or a t-butoxycarbonyl group is preferable.

The introduction of the substituent B is carried out via the acidic functional group of the resin (A), and the substituent B is preferably 15 to 100%, more preferably the total acidic functional group of the resin (A). Is introduced at 30 to 100%. The Mw of the resin (B) measured by GPC is preferably 1,000 to 150,
000, particularly preferably 3,000 to 100,000.

The resin (B) is insoluble or sparingly soluble in alkali. Alkali sparingly soluble is the same as the case of using a film of only the resin (B) in place of the resist film under suitable alkali developing conditions when forming a pattern on the resist film formed by using the second invention. When the alkali development is carried out, it means the property that the resin (B) has a film thickness of 50% or more of the initial film thickness and remains after the operation.

Acid Forming Agent The acid forming agent used in the present invention is, for example, an onium salt, a halogen-containing compound, a quinonediazide compound, a sulfone compound, a nitrobenzyl compound, a sulfonic acid compound, and the like. It can be illustrated.

Examples of the onium salt include iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, ammonium salt and the like, and the following formula (5) is preferable.

[0030]

[Chemical 5]

A compound represented by the following formula (6)

[0032]

[Chemical 6]

A compound represented by the following formula (7)

[0034]

[Chemical 7]

Examples thereof include compounds represented by:

Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound, and preferably the following formula (8)

[0037]

[Chemical 8]

A compound represented by the following formula (9)

[0039]

[Chemical 9]

Examples thereof include compounds represented by:

Examples of the quinonediazide compound include diazobenzoquinone compounds and diazonaphthoquinone compounds, and the following formula (10) is preferable.

[0042]

[Chemical 10]

A compound represented by the following formula (11)

[0044]

[Chemical 11]

A compound represented by the following formula (12)

[0046]

[Chemical 12]

A compound represented by the following formula (13)

[0048]

[Chemical 13]

Examples thereof include compounds represented by:

Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone and the like, preferably the following formula (14):

[0051]

[Chemical 14]

Examples thereof include compounds represented by:

Examples of the nitrobenzyl compound include a nitrobenzyl sulfonate compound and a dinitrobenzyl sulfonate compound, and the following formula (15) is preferable.

[0054]

[Chemical 15]

Examples thereof include compounds represented by:

Examples of the sulfonic acid compound include alkyl sulfonic acid ester, haloalkyl sulfonic acid ester, aryl sulfonic acid ester, imino sulfonate and the like, and the following formula (16) is preferable.

[0057]

[Chemical 16]

A compound represented by the following formula (17)

[0059]

[Chemical 17]

A compound represented by the following formula (18)

[0061]

[Chemical 18]

Examples thereof include compounds represented by:

Of these, onium salts and quinonediazide compounds are particularly preferable. The compounding amount of these acid forming agents is preferably 1 to 70 parts by weight, more preferably 3 to 50 parts by weight, and further preferably 3 to 100 parts by weight of the resin (A) or the resin (B). 20 parts by weight. If it is less than 1 part by weight, it is difficult to obtain sufficient pattern forming ability, and if it exceeds 70 parts by weight, scum tends to occur.

Dissolution Control Agent In the first invention, a dissolution control agent is used. The dissolution control agent itself has an effect of controlling the alkali solubility of the resin (A), and is decomposed in the presence of an acid, for example, hydrolyzed to reduce the alkali solubility control effect of the resin (A). It is a compound that exhibits the property of disappearing or the property of promoting the alkali solubility of the resin (A).

Examples of the dissolution control agent include compounds in which a substituent capable of being liberated in the presence of an acid is introduced into an acidic functional group. Examples of the substituent include the substituent B described in the resin (B).

The dissolution controlling agent may be a low molecular weight compound or a high molecular weight compound. For example, the following formula (19) and formula (2
0), formula (21), formula (22) and formula (23)

[0067]

[Chemical 19]

[0068]

[Chemical 20]

[0069]

[Chemical 21]

[0070]

[Chemical formula 22]

[0071]

[Chemical formula 23]

Examples thereof include compounds represented by and resins (A) which have a substituent B introduced therein (hereinafter referred to as "resin C").

The compounding amount of the dissolution control agent is preferably 5 to 100 parts by weight of the resin (A) in the first invention.
150 parts by weight, more preferably 5 to 100 parts by weight.

Crosslinking Agent In the third invention, a crosslinking agent is used. The cross-linking agent is an acid,
For example, resin (A) in the presence of an acid generated by irradiation with radiation
Is a compound that crosslinks. The cross-linking agent is not particularly limited as long as it is a compound having the above-mentioned properties, and for example, an aromatic compound having a cross-linkable substituent can be mentioned as a preferable example.

Examples of the substituent capable of carrying out the crosslinking reaction include a -C (R ⁴⁴ R ⁴⁵ ) -OR ⁴⁶ group [(wherein R ⁴⁴ and R ⁴⁵ are the same or different and each is a hydrogen atom or a carbon number of 1 to 4). R ⁴⁶ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, an aralkyl group, —NR ⁴⁷ R ⁴⁸
A group (provided that R ⁴⁷ and R ⁴⁸ are the same or different,
An alkyl group having 1 to 4 carbon atoms, a cyclo ring having 3 to 8 atoms containing or not containing a hetero atom), -COR ⁴⁹
A group (provided that R ⁴⁹ is an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 14 carbon atoms)],

-CO-R ⁵⁰ group (provided that R ⁵⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), -CR ⁵¹ =
A CR ⁵² R ⁵³ group (provided that R ⁵¹ , R ⁵² and R ⁵³ are the same or different and each is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) and the like.

Specific examples of these crosslinkable substituents include glycidyl ether group, glycidyl ester group, glycidylamino group, methoxymethyl group, ethoxymethyl group, benzyloxymethyl group, dimethylaminomethyl group and diethoxymethyl group. Examples thereof include an amino group, a morpholinomethyl group, an acetoxymethyl group, a benzoyloxymethyl group, a formyl group, an acetyl group, a vinyl group and an isopropenyl group.

Examples of the aromatic compound having a substituent include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, novolac type epoxy compounds, resole resin type epoxy compounds, polyhydroxystyrene type epoxy compounds. , A methylol group-containing melamine compound, a methylol group-containing benzoguanamine compound, a methylol group-containing urea compound, a methylol group-containing phenol compound, a methylol group-containing melamine compound, a methylol group-containing phenol compound, an alkyl ether group-containing melamine compound,
Alkyl ether group-containing benzoguanamine compound, alkyl ether group-containing urea compound, alkyl ether group-containing phenol compound, alkyl ether group-containing melamine compound, alkyl ether group-containing phenol compound,
Examples thereof include a carboxymethyl group-containing melamine compound, a carboxymethyl group-containing benzoguanamine compound, a carboxymethyl group-containing urea compound, a carboxymethyl group-containing phenol compound, a carboxymethyl group-containing melamine compound, and a carboxymethyl group-containing phenol compound.

Of these, a methylol group-containing phenol compound, a methylol group-containing phenol compound, a methoxymethyl group-containing melamine compound, a methoxymethyl group-containing phenol compound and an acetoxymethyl group-containing phenol compound are preferable.

As the cross-linking agent, those obtained by modifying the resin (A) with the above-mentioned substituent capable of cross-linking reaction to impart the property as the cross-linking agent can be advantageously used. In that case, the introduction rate of the substituent is usually 5 to 60%, preferably 10 to 50% with respect to the total amount of the acidic functional groups of the resin (A),
It is more preferably adjusted to 15 to 40%. If it is 5% or less, it is difficult to cause a sufficient cross-linking reaction, and the film remaining rate is lowered, and the pattern is meandered or swollen. On the other hand, when it is 60% or more, the alkali solubility of the resin (A) is lowered, and the developability tends to be deteriorated.

The blending amount of the crosslinking agent is preferably 5 to 95 parts by weight, particularly preferably 15 to 85 parts by weight, and further preferably 20 to 75 parts by weight with respect to 100 parts by weight of the resin (A). If the amount is 5 parts by weight or less, it is difficult to cause a sufficient crosslinking reaction, and the reduction of the residual film rate, the meandering of the pattern, and the swelling are likely to occur. On the other hand, if the amount is 95 parts by weight or more, the scum content is large and the developability tends to deteriorate.

Having a nitrogen-containing basic group and acidic group in the molecule
The compound having a nitrogen-containing basic group and an acidic group in the molecule used in the present invention is preferably at least one structure and at least one structure represented by the following formulas (24) to (28). Is a compound having the acidic group of 1) in the same molecule. More preferably, the acidic group is a carboxyl group,
It is a compound having a sulfo group or a phenolic hydroxyl group.

[0083]

[Chemical formula 24]

Here, specific examples of the compound having a nitrogen-containing basic group and a carboxyl group in the molecule include nicotinic acid, isoleucine, glycine, glutamic acid, threonine, theanine, tryptophan, L-valine, histidine hydrochloride, phenylalanine. , Methionine, folic acid, lysine, aspartate, glutamate, 3-aminopyrazine-2-carboxylic acid and the like.

Specific examples of the compound having a nitrogen-containing basic group and a sulfo group in the molecule include thiamine naphthalene disulfonate, thiamine naphthalene lauryl sulfate, and 3
-Pyridine sulfonic acid etc. can be mentioned

Further, specific examples of the compound having a nitrogen-containing basic group and a phenolic hydroxyl group in the molecule include 2-
Hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2-amino-p-cresol, 5-
Amino-o-cresol, 6-amino-m-cresol and the like can be mentioned. Particularly preferred compounds are nicotinic acid, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine and the like.

The compound having a nitrogen-containing basic group and an acidic group in the molecule can be used together with a nitrogen-containing basic compound having no acidic group.

The amount of the compound having a nitrogen-containing basic group and an acidic group in the molecule is 1 (A) resin or (B) 1 resin.
The amount is usually 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 00 parts by weight. If it is less than 0.001 part by weight, the pattern shape and adhesiveness tend to be deteriorated, whereas if it exceeds 10 parts by weight, the sensitivity is lowered and the developability of the radiation-irradiated portion is apt to be deteriorated.

The composition of the present invention may further contain various additives, if desired. Examples of such an additive include a surfactant for improving coating properties, striation and developability of a radiation irradiated portion after formation of a dry coating film. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and commercial products. For example, F top EF301, EF303,
EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Megafax F
171, F173 (manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC430, FC431 (Sumitomo 3M Limited)
Made), Asahi Guard AG710, Surflon S-38
2, SC101, SC102, SC103, SC10
4, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (co)
Polymers such as Polyflow No. 75 and No. 95 (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) are used.

The content of the surfactant is usually 2 parts by weight or less per 100 parts by weight of the resin (A) or the resin (B). Examples of other additives include antihalation agents, adhesion promoters, safety stabilizers, and defoamers.

The composition of the present invention comprises the above-mentioned components and various additives to be blended if necessary, in the required amounts,
It is prepared by dissolving in a solvent.

Examples of the solvent used in this case include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, and diethylene glycol. -Diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate , Propylene glycol monopropyl ether acetate, toluene, xylene, methyl ethyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexane Sanon, 2-hydroxypropionic acid methyl, ethyl 2-hydroxypropionate, 2-hydroxy-2-methylpropionic acid ethyl, ethyl ethoxy acetate, hydroxyethyl acetate, 2-hydroxy-3
-Methyl methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-
Methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, pyruvin Methyl acid, ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylformamide, N, N
-Dimethylacetamide and the like can be mentioned.

If necessary, these solvents may be benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol ether.
Rumonoethyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-
Nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate,
γ-butyrolactone, ethylene carbonate, propylene carbonate,
A high boiling point solvent such as phenyl cellosolve acetate can also be added.

The composition of the present invention is applied in the form of the above solution onto a substrate such as a silicon wafer and dried to form a resist film. In this case, for coating on a substrate, for example, the composition of the present invention is dissolved in the above solvent so that the solid content concentration is 5 to 50% by weight, filtered, and then spin-coated, flow-coated, spin-coated. It is performed by applying a coating method such as a coating method.

The formed resist film is partially irradiated with radiation to form a fine pattern. The radiation used is not particularly limited and includes, for example, deep ultraviolet rays such as excimer laser, X-rays such as synchrotron radiation,
Radiation such as a charged particle beam such as an electron beam is used depending on the type of acid former used. Irradiation conditions such as radiation dose are appropriately determined depending on the composition of the composition, the type of each additive, and the like.

In the present invention, in order to improve the apparent sensitivity and the like of the resist, it is preferable to perform heating after irradiation with radiation. The heating conditions differ depending on the composition of the composition, the type of each additive, etc.
The temperature is 30 to 200 ° C, preferably 50 to 150 ° C.

Examples of the developer used for the subsequent development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate,
Ammonia water, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, An alkaline aqueous solution prepared by dissolving 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonane and the like can be used.

Further, an alkaline aqueous solution prepared by appropriately adding a water-soluble organic solvent, for example, alcohols such as methanol and ethanol and a surfactant to the above developing solution can be used as the developing solution.

[0099]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
In the examples, various characteristics were determined as follows.

[0100] The optimum exposure dose was determined so that a line and space of 0.4 µm could be formed into a pattern as designed. The minimum size of lines and spaces separated when the optimum exposure amount for resolution was given was obtained. Using the pattern scanning electron microscope, the lower side length A and the upper side length B of the rectangular cross section of the resist pattern are measured, and 0.85 ≦ B / A ≦
When it was 1, the pattern shape was judged to be good.
However, in the case where the pattern shape has a skirt or an inverse taper shape, it was determined that the pattern was defective even if B / A was within the above range.

Focus Tolerance The range of defocus that can maintain the good pattern shape defined above was obtained when exposure was performed with the focus of the stepper shifted. Lithography process stability After exposure, the substrate was left for 2 hours and then post-exposure baked to evaluate the optimum exposure dose and pattern shape. The degree of peeling of the resist pattern was examined using an adhesive scanning electron microscope.

Mw: Tosoh GPC column (G200
0H _XL 2 this, one G3000H _XL, G4000 _XL 1
The present invention) was used, and the flow rate was 1.0 ml / min, the elution solvent was tetrahydrofuran, and the column temperature was 40 ° C.

Example 1 30 g of polyhydroxystyrene was dissolved in tetrahydrofuran, 10 g of potassium t-butoxide was added, and 75 g of di-t-butyl carbonate was added at 0 ° C. with stirring.
g was added dropwise and reacted for 6 hours. After the reaction was completed, this solution was added dropwise to water, and the precipitated polymer was dried in a vacuum drier.
Dry overnight at 0 ° C. The obtained polymer has Mw = 3
From the result of NMR measurement, it was a structure in which 63% of hydrogen of the phenolic hydroxyl group was substituted with a t-butoxycarbonyl group at 000 and Mw / Mn = 1.60.

10 g of this polymer, 0.2 g of triphenylsulfonium trifluoromethanesulfonate and 0.03 g of nicotinic acid were dissolved in 31 g of methyl 3-methoxypropionate and then filtered through a 0.2 μm filter to prepare a composition solution. .. The prepared composition solution was spin-coated on a silicon wafer and then baked at 100 ° C. for 2 minutes to form a resist film having a thickness of 1.0 μm.

An excimer laser having a wavelength of 248 nm is applied to the formed resist film at 20 mJ.c by using a stepper.
After m ^-2 irradiation, post exposure bake at 90 ° C for 2 minutes,
It was developed with an aqueous tetramethylammonium hydroxide solution for 60 seconds at 23 ° C. and then rinsed with water for 30 seconds. The formed positive pattern gave good results as shown in Table 1. Furthermore, this positive pattern is 1
When heated for 2 minutes on a hot plate at 50 ° C., no change in pattern shape was observed.

Comparative Example 1 Pattern formation was performed in the same manner as in the composition solution used in Example 1, except that a composition solution containing no nicotinic acid was prepared and the irradiation amount of the excimer laser was changed. The results are shown in Table 1.

Example 2 54 g of polyhydroxystyrene was dissolved in acetone,
27 g of t-butyl-α-bromoacetic acid, potassium carbonate 10
g and 9 g of potassium iodide were added, and the mixture was reacted for 7 hours with stirring under reflux. After completion of the reaction, this solution was dropped into water, and the precipitated polymer was dried in a vacuum drier.
Dry overnight at 0 ° C. The obtained polymer has Mw = 1.
At 8,000 and Mw / Mn = 1.87, it was a structure in which 22% of hydrogen of the phenolic hydroxyl group was substituted with t-butylacetic acid residue from the result of NMR measurement.

10 g of this polymer, 0.1 g of triphenylsulfonium trifluoromethanesulfonate and 0.04 g of 2-hydroxypyridine were dissolved in 31 g of methyl 3-methoxypropionate and then filtered through a 0.2 μm filter to obtain a composition solution. Prepared. After spin coating the prepared composition solution on a silicon wafer,
Baking was performed at 0 ° C. for 2 minutes to form a resist film having a thickness of 1.0 μm.

An excimer laser with a wavelength of 248 nm was used at 25 mJ.c for the formed resist film using a stepper.
After irradiating m ^-2 , it is post-exposure baked at 100 ° C for 2 minutes, and then exposed to an aqueous tetramethylammonium hydroxide solution for 6 minutes.
It was developed for 0 seconds at 23 ° C. and then rinsed with water for 30 seconds. The formed positive pattern gave good results as shown in Table 1. Furthermore, when this positive pattern was heated on a hot plate at 150 ° C. for 2 minutes,
No change in pattern shape was observed.

Comparative Example 2 In the composition solution used in Example 2, a composition solution was prepared in which 2-hydroxypyridine was not added and pattern formation was attempted in the same manner. An insoluble layer was formed and a pattern could not be formed.

Example 3 107 g of a copolymer of maleic acid and styrene was dissolved in ethyl acetate to obtain 50 g of 3,4-dihydro-2H-pyran.
And p-toluenesulfonic acid 0.1 g were added, and the mixture was stirred while
The reaction was carried out at 5 ° C for 3 hours. After the reaction was completed, this solution was mixed with distilled water, p-toluenesulfonic acid was extracted using a separating funnel, and then dropped into hexane, and the precipitated polymer was dried in a vacuum dryer at 50 ° C. overnight. did. The obtained polymer has Mw = 11,000 and Mw / Mn =
According to the result of NMR measurement in 2.1, 52% of the carboxylic acid of maleic acid had a structure in which it was substituted with a tetrahydropyranyl group.

10 g of this polymer, 0.2 g of triphenylsulfonium hexafluoroantimonate and 0.03 g of nicotinic acid were added to methyl 3-methoxypropionate 3
After dissolving in 1 g, it was filtered through a 0.2 μm filter to prepare a composition solution. The prepared composition solution was spin-coated on a silicon wafer and then baked at 100 ° C. for 2 minutes to form a resist film having a thickness of 1.0 μm.

An excimer laser having a wavelength of 248 nm is applied to the formed resist film with a stepper at 35 mJ.c.
After m ^-2 irradiation, post exposure bake at 90 ° C for 2 minutes,
It was developed with an aqueous tetramethylammonium hydroxide solution for 60 seconds at 23 ° C. and then rinsed with water for 30 seconds. The formed positive pattern gave good results as shown in Table 1. Furthermore, this positive pattern is 1
When heated for 2 minutes on a hot plate at 40 ° C., no change in pattern shape was observed.

Comparative Example 3 Pattern formation was performed in the same manner as in Example 3 except that a composition solution containing no nicotinic acid was prepared from the composition solution used in Example 3 and the irradiation amount of the excimer laser was changed. went. The results are shown in Table 1.

Example 4 54 g of cresol (m- / p- = 6/4) novolak was dissolved in acetone to give t-butyl-α-bromoacetic acid 27.
g, 10 g of potassium carbonate and 9 g of potassium iodide were added, and the mixture was reacted for 7 hours while continuing reflux with stirring.
After the reaction was completed, this solution was dropped into water, and the precipitated polymer was dried in a vacuum dryer at 50 ° C. overnight. The polymer obtained had Mw = 5,600, Mw / Mn = 4.8, N
22% of hydrogen of phenolic hydroxyl group from the result of MR measurement
Was a structure substituted with a t-butylacetic acid residue.

10 g of this polymer, 0.1 g of triphenylsulfonium trifluoromethanesulfonate and 0.02 g of nicotinic acid were dissolved in 31 g of methyl 3-methoxypropionate and then filtered through a 0.2 μm filter to prepare a composition solution. .. The prepared composition solution was spin-coated on a silicon wafer and then baked at 90 ° C. for 2 minutes to form a resist film having a thickness of 1.0 μm.

A stepper is used for the formed resist film and an excimer laser having a wavelength of 248 nm is used at 30 mJ / c.
After irradiating m ^-2 , it is post-exposure baked at 100 ° C for 2 minutes, and then exposed to an aqueous tetramethylammonium hydroxide solution for 6 minutes.
It was developed for 0 seconds at 23 ° C. and then rinsed with water for 30 seconds. The formed positive pattern gave good results as shown in Table 1. Furthermore, when this positive pattern was heated on a hot plate at 150 ° C. for 2 minutes,
No change in pattern shape was observed.

Comparative Example 4 As a composition solution, 10 g of the polymer used in Example 4 and 1,2,3,4,4'-tetrahydroxybenzophenone
20 g of 2-naphthoquinonediazide-4-sulfonic acid ester (esterification rate 70%) was dissolved in 34 g of methyl 3-methoxypropyleneate and then filtered through a 0.2 μm filter to prepare a composition solution. A resist film was formed in the same manner, exposed in the same manner, and similarly developed and rinsed. The results are shown in Table 1.

Example 5 10 g of polyhydroxystyrene (Mw = 9000),
After dissolving 4 g of 2,6-bismethylol-p-cresol, 0.3 g of triphenylsulfonium trifluoromethanesulfonate and 0.03 g of L-phenylalanine in 31 g of methyl 3-methoxypropionate, 0.2
A composition solution was prepared by filtering with a μm filter. The prepared composition solution was spin-coated on a silicon wafer and then baked at 90 ° C. for 2 minutes to give a film thickness of 1.0.
A μm resist film was formed.

An excimer laser with a wavelength of 248 nm is applied to the formed resist film with a stepper at 20 mJ.c.
After irradiating m ^-2 , it is post-exposure baked at 100 ° C for 2 minutes, and then exposed to an aqueous tetramethylammonium hydroxide solution for 6 minutes.
It was developed for 0 seconds at 23 ° C. and then rinsed with water for 30 seconds. The negative pattern formed gave good results as shown in Table 1. Furthermore, when this negative pattern was heated on a hot plate at 150 ° C. for 2 minutes,
No change in pattern shape was observed.

Comparative Example 5 Pattern formation was carried out in the same manner as in Example 5 except that the composition solution used in Example 5 was prepared without adding L-phenylalanine and the excimer laser irradiation amount was changed. I went. The results are shown in Table 1. 5 mJ.
A line-and-space pattern of 0.4 μm was resolved when irradiated with cm ⁻² , but foreign matter (particulate projections with a diameter of about 0.02 to 0.05 μm) on the pattern surface.
Was generated, and the shape was unfavorable for fine processing.

Example 6 Poly (4-hydroxystyrene) (Mw = 34,000)
0) 50 g was reacted with hexamethyldisilazane in methyl 3-methoxy-2-propionate at 90 ° C. for 6 hours.
After completion of the reaction, the solution was concentrated under reduced pressure to prepare a polymer concentration of 20% by weight. The obtained polymer solution is NM
As a result of measurement by R, the polymer in the solution had a structure in which 40% of the phenolic hydroxyl group of poly (4-hydroxystyrene) was protected by a trimethylsilyl group. After dissolving 0.06 g of triphenylsulfonium trifluoromethanesulfonate and 0.01 g of nicotinic acid in 10 g of this solution, the solution was filtered through a 0.2 μm filter to obtain a composition solution. The obtained composition solution was spin-coated on a silicon wafer and then baked at 110 ° C. for 2 minutes to form a resist film having a thickness of 1.0 μm.

A KrF excimer laser having a wavelength of 248 nm is used for 30 m by using a stepper on the formed resist film.
After irradiation with J.cm ^-2, post exposure bake, development and rinsing were performed in the same manner as in Example 1. The formed positive pattern gave good results as shown in Table 1.

Comparative Example 6 In the composition solution used in Example 6, a composition solution in which nicotinic acid was not added was prepared, a resist film was formed in the same manner, exposure was carried out in the same manner, and then development and rinsing were carried out in the same manner. I went. The results are shown in Table 1. A line-and-space pattern of 0.35 μm was resolved when irradiated with 5 mJ.cm ^-2 , but the interval from exposure to post-exposure bake was 2
When the time was set, an insoluble layer was formed on the surface and the pattern could not be resolved.

[0125]

[Table 1]

[0126]

According to the present invention, there is no swelling by a developing solution, and it is excellent in developability, pattern shape, focus tolerance, heat resistance, adhesiveness, lithographic process stability, etc., and has high resolution and high sensitivity. It is possible to obtain a radiation-sensitive resin composition suitable as a resist that can be applied to a radiation source.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical indication location H01L 21/027 (72) Inventor Takao Miura 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. Within

Claims (3)

[Claims] 1. An alkali-soluble resin, (2) a radiation-sensitive acid forming agent, (3) a property of controlling the alkali solubility of the alkali-soluble resin of (1), and in the presence of an acid. A compound which is decomposed to exhibit the property of reducing or eliminating the alkali solubility control effect of the alkali-soluble resin of (1) or the property of promoting the alkali solubility of the alkali-soluble resin of (1), and (4) in the molecule A positive-type radiation-sensitive resin composition comprising a compound having a nitrogen-containing basic group and an acidic group. 2. An alkali-insoluble or sparingly-soluble resin having (1) at least one acid-dissociable group selected from a substituted methyl group, a 1-substituted ethyl group, a germyl group, an alkoxycarbonyl group, an acyl group and a silyl group. A resin which is alkali-soluble when the above groups are acid-dissociated, (2)
A positive radiation-sensitive resin composition comprising a radiation-sensitive acid forming agent and (3) a compound having a nitrogen-containing basic group and an acidic group in the molecule. 3. (1) an alkali-soluble resin, (2) a radiation-sensitive acid forming agent, (3) a compound which cross-links the alkali-soluble resin of (1) in the presence of an acid, and (4) a compound contained in the molecule. A negative-type radiation-sensitive resin composition comprising a compound having a nitrogen basic group and an acidic group.