JP2001133977A - Multilayer photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a two-layer photosensitive material having superior sensitivity and resolution and giving a resist pattern having low edge roughness and a good cross-sectional shape in the formation of a minute resist pattern of <=200 nm and a three-layer photosensitive material less liable to form a T-shaped cross section and giving a resist pattern having no trailing, low edge roughness and a good cross-sectional shape. SOLUTION: A water-insoluble antireflection layer having 30-300 nm thickness is disposed on a substrate, a negative type resist layer having 200-500 nm thickness is disposed on the antireflection layer and a water-soluble antireflection layer is further disposed on the resist layer if necessary to obtain the objective multilayer photosensitive material. The negative type resist layer contains (A) an alkali-soluble resin, (B) an onium salt which generates an acid when irradiated and (C) glycolic uryl whose N position has been substituted by at least one crosslink forming group selected from hydroxyalkyl and lower alkoxyalkyl groups. The amounts of the components B and C are 0.5-20 parts by mass and 3-50 parts by mass, respectively, based on 100 parts by mass of the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
A thin water-insoluble antireflection layer of 0 to 300 nm is provided,
Furthermore, a thin negative resist layer having a thickness of 200 to 500 nm is provided thereon, and if necessary, the composition of the negative resist layer is modified for a multilayer photosensitive material having a water-soluble antireflection layer provided thereon. The present invention relates to a photosensitive material which has excellent sensitivity and resolution and is improved so as to provide a resist pattern having a good sectional shape with a small edge roughness.

[0002]

2. Description of the Related Art Recently, in response to a demand for miniaturization of a semiconductor device, an alkali-developable chemical having a resolution necessary for obtaining a resist pattern of about 250 nm and a resist pattern of 200 nm or less for the next generation. Amplification type negative resist photosensitive materials are being developed.

A chemically amplified negative resist is obtained by adding an acid generator to an acid-curable resin component comprising a combination of an alkali-soluble phenol resin and an aminoplast such as urea-formaldehyde adduct or melamine-formaldehyde adduct. It is known that the compound is blended, but by using such a negative resist on a substrate provided with an organic or inorganic antireflection layer, the resolution is dramatically improved, so that the thickness is 200 nm or less. When a resist pattern is formed, it is often used in combination with such an antireflection layer.

However, for example, the "DUV series"
When used in combination with an organic anti-reflection layer such as (manufactured by Brewer Science) and a negative resist, a pattern having a good cross-sectional shape may not be obtained. Even when the resist pattern is used in combination with a prevention layer, there is a demand for a resist pattern having a good rectangular cross-sectional shape that does not exhibit a tapered shape or a skirt shape. In addition, the antireflection film also includes an inorganic antireflection film formed by chemical vapor deposition (CVD). However, in this case, there is a similar problem. I have. In addition, when forming an ultrafine resist pattern having a resist pattern size of 200 nm or less, an undesirable phenomenon called “edge roughness” may be accompanied,
Suppressing this has emerged as a new problem to be solved.

On the other hand, in the case of a chemically amplified positive or negative resist, by providing a water-soluble antireflection layer on the resist layer, the resolution is improved and the influence of standing waves is suppressed. (Patent No. 2
878150). However, when an organic or inorganic anti-reflection layer is provided below the resist layer, and a water-soluble anti-reflection layer is simultaneously provided thereon to form a three-layer structure. A removal step and an etching step for this antireflection layer are required,
In the manufacture of semiconductor devices requiring high throughput, there is a drawback that the operation becomes complicated, and therefore, in general, any one of a lower layer and a resist layer composed of the antireflection layer or an upper layer and a resist layer composed of the water-soluble antireflection layer is required. That two-layer structure was chosen.

In the case of a two-layer structure in which a water-soluble antireflection layer is provided on a negative resist layer, an unnecessary crosslinking reaction occurs near the interface between the negative resist layer and the water-soluble antireflection layer. Since a resist pattern having a T-shaped cross section is easily formed and a resist pattern having good cross-sectional perpendicularity without the influence of standing waves has been desired in recent years, anti-reflection of the negative resist layer and the lower layer has been desired. A three-layer structure that suppresses skirting at the interface with the layer and suppresses the occurrence of a T-shaped cross section at the interface between the negative resist and the upper water-soluble anti-reflective layer, giving an excellent rectangular cross-section pattern shape Has come to the spotlight.

[0007]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides a method for forming a fine resist pattern of 200 nm or less, in addition to excellent sensitivity and resolution, a good cross-section with little edge roughness. A two-layer multi-layer photosensitive material that gives a resist pattern of a shape and a three-layer multi-layer photosensitive material that gives a resist pattern with a good cross-sectional shape in which the occurrence of a T-shaped cross section is suppressed, there is no skirting, and there is little edge roughness. It was made for the purpose of providing.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies on a multilayer photosensitive material particularly suitable for forming a fine resist pattern, and as a result, a water-insoluble antireflection film having a predetermined thickness is formed on a substrate. A layer having a thickness of 200 to 500 n
m in a two-layer structure provided with a negative resist layer, or a three-layer structure having a water-soluble anti-reflection layer provided thereon if necessary, wherein the negative resist layer has a specific chemical composition. Based on this finding, it was found that by using an amplified resist, it was possible to obtain a resist pattern with excellent sensitivity, resolution, and a good rectangular cross section with little edge roughness regardless of the multilayer structure. The present invention has been made.

That is, according to the present invention, the thickness of 30 to
A multi-layer photosensitive composition comprising a water-insoluble antireflection layer having a thickness of 300 nm, a negative resist layer having a thickness of 200 to 500 nm provided thereon, and a water-soluble antireflection layer further provided on the negative resist layer as required. The negative resist layer is formed of at least one selected from (A) an alkali-soluble resin, (B) an onium salt that generates an acid upon irradiation with radiation, and (C) a hydroxyalkyl group and a lower alkoxyalkyl group. The glycoluril substituted at the N-position by the cross-linking group of (B) in a proportion of 0.5 to 20 parts by mass of the component (B) and 3 to 50 parts by mass of the component (C) per 100 parts by mass of the component (A). A photosensitive material characterized by the following.

Although it has been known to use tetramethoxymethylated glycoluril as a cross-linking agent component of a negative resist, a water-insoluble antireflection layer or a multi-layer photosensitive film having this and a water-soluble antireflection layer has been known. It was quite unexpected to use this in a material to give a resist pattern with low edge roughness and good rectangular cross section.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The substrate of the present invention can be arbitrarily selected from materials conventionally used for substrates for electronic parts and electric parts. Such materials include, for example, silicon wafers and Si wafers.
Examples include a silicon wafer covered with ON, SiN, Si ₃ N ₄ , polycrystalline silicon, TiN, and the like, and a glass plate covered with a metal such as tantalum and chromium.

Next, the water-insoluble antireflection layer provided on the substrate may be inorganic or organic. The inorganic anti-reflection layer is usually formed by a chemical vapor deposition method, that is, CVD. The organic antireflection layer is a coating solution prepared by dissolving a two-component antireflection layer forming component of a resin component for film formation and an antireflection component or a one-component antireflection layer forming component in which the resin itself has antireflection ability in an organic solvent. It is formed by applying to a substrate surface, drying and heating. The thickness of this layer is usually selected within the range of 30 to 300 nm. The coating liquid for forming an organic antireflection layer used in the present invention is a commercially available product, for example, “D
UV series "(manufactured by Brewer Science).

When a resist pattern is formed using a photosensitive material having a negative resist layer formed on a water-insoluble antireflection layer formed using these coating solutions, the bottom of the resist pattern may be formed. But this is
It is considered that the acid component is leached from the water-insoluble antireflection layer during the heat treatment after the exposure. Further, according to the present invention, even when a water-insoluble antireflection layer having a large content of an acid component is used, a particularly remarkable effect is exhibited in that skirting is prevented.

On the other hand, the water-soluble antireflection layer used in the present invention is for suppressing the resolution of the resist pattern and the influence of standing waves, and comprises a water-soluble resin component such as polyvinylpyrrolidone and polyvinyl alcohol. Perfluorooctylsulfonic acid, perfluoroalkylsulfonic acid such as perfluorodecylsulfonic acid, ammonium salt of perfluorocarboxylic acid such as perfluoroheptanoic acid or perfluorooctanoic acid, tetramethylammonium hydroxide salt or monoethanolamine An aqueous solution containing a fluorine-based surfactant component such as a salt is applied on a negative resist layer and dried. The thickness of this water-soluble antireflection layer is preferably in the range of 35 to 45 nm.

In the present invention, as the negative resist, (A) an alkali-soluble resin, (B) a substance capable of generating an acid upon irradiation with an active ray selected from onium salts, (C) a hydroxyalkyl group and a lower alkyl group. It contains, as an essential component, glycoluril substituted at the N-position with at least one cross-linking group selected from an alkoxyalkyl group, and optionally further comprises (D) an aliphatic lower amine or (E) an organic carboxylic acid or phosphorus. It is necessary to use a compound containing oxo acid or a derivative thereof, or both.

At this time, the alkali-soluble resin used as the component (A) is not particularly limited, and can be arbitrarily selected from chemical amplification type alkali-soluble resin components. In terms of giving a good resist pattern with a cross-sectional shape, the mass average molecular weight is from 2,000 to
4,000 copolymer of 60-97 mol% of hydroxystyrene and 40-3 mol% of styrene, in which 5-30% of the hydrogen atoms present in the hydroxyl groups are substituted by alkali-insoluble groups, and the weight average molecular weight is 2 6,000-4,000 hydroxystyrene 60-97 mol% and styrene 40-3
Mol% of the copolymer, 3 to 40% of the hydroxyl groups present therein.
% Of hydrogen atoms is substituted with an alkali-insoluble group, and polyhydroxystyrene having a weight average molecular weight of 2,000 to 4,000 is preferred. In particular, in terms of providing a resist pattern having a rectangular cross-sectional shape, the mass average molecular weight is from 2,000 to
A copolymer of 4,000 hydroxystyrene at 60-97 mol% and styrene at 40-3 mol% is preferred.

The above-mentioned alkali-insoluble group is a substituent that reduces the alkali solubility of an unsubstituted alkali-soluble resin. For example, a tert-butoxycarbonyl group, t
There are tertiary alkoxycarbonyl groups such as tert-amyloxycarbonyl group, and lower alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group. Among them, a lower alkyl group, particularly an isopropyl group, is preferable because it is hardly affected by the surrounding environment where the resist patterning is performed and a good resist pattern is obtained.

Next, the component (B), that is, the acid generator,
It is a compound that generates an acid upon irradiation with radiation, which is generally used as a component of a chemically amplified resist. In the present invention, it is preferable to use an onium salt containing an alkylsulfonic acid ion as an anion. Such acid generators are already known and are described, for example, in JP-A-54-95686 and JP-A-62-22994.
No. 2, JP-A-2-120366 and the like.

To date, tris (2,3-tris) has been used as an acid generator for a negative resist for KrF because of its advantages of providing a resist pattern having high transparency to KrF laser light and excellent resolution. Dibromopropyl)
Isocyanurate was considered to be preferable (Japanese Patent Publication 8-
No. 3635). However, when such a halogen acid generator is used in combination with a glycoluril-based crosslinking agent, there is a drawback that a resist pattern cannot be formed with a sensitivity applicable in an actual line process of LSI manufacturing.

In addition, a sulfonic acid generator such as bis (cyclohexylsulfonyl) diazomethane is also known. However, when this is used in combination with a glycoluril-based cross-linking agent, a high-resolution resist pattern can be obtained. Can not. However, an onium salt having a fluorinated alkylsulfonate ion as an anion was used in combination with a crosslinking agent consisting of glycoluril substituted at the N-position with at least one crosslinking forming group selected from a hydroxyalkyl group and a lower alkoxyalkyl group. In this case, there is no such a disadvantage as described above that occurs when another acid generator is used, and a resist layer having excellent characteristics is provided.

The anion of the component (B) is a fluoroalkyl sulfonate ion in which some or all of the hydrogen atoms of the alkyl group have been fluorinated. As the number of carbon atoms increases and the fluorination rate (the ratio of fluorine atoms in the alkyl group) decreases, the strength of the sulfonic acid decreases. Therefore, all of the hydrogen atoms of the alkyl group having 1 to 10 carbon atoms are fluorinated. Preferred are fluorinated alkyl sulfonic acids.

On the other hand, the cation which is combined with the anion to constitute the acid generator can be arbitrarily selected from those conventionally used in this type of acid generator.
There is no particular limitation. These include, for example, methyl, ethyl, propyl, n-butyl, tert
A lower alkyl group such as -butyl group or a methoxy group, which may be substituted with a lower alkoxy group such as an ethoxy group, or an unsubstituted diphenyliodonium or triphenylsulfonium, a di-lower alkylmonophenylsulfonium, Lower alkylcyclohexyl 2-
Oxocyclohexylsulfonium and the like.

Particularly preferred as this cation are those represented by the general formula

Embedded image (R ¹ and R ² in the formula are each a hydrogen atom, and each has 1 to 4 carbon atoms.
Which is an alkyl group or an alkoxyl group having 1 to 2 carbon atoms, for example, diphenyliodonium, bis (4-tert-butylphenyl) iodonium, etc.

Embedded image (Wherein R ³ , R ⁴ and R ⁵ are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxyl group having 1 to 2 carbon atoms), for example, triphenylsulfonium, tris (4 General formulas such as -methylphenyl) sulfonium and tris (4-methoxyphenyl) sulfonium

Embedded image Wherein R ⁶ is an alkyl group having 1 to 4 carbon atoms, such as dimethylphenylsulfonium;

Embedded image Wherein R ⁶ is the same as described above, for example, methylcyclohexyl-2-oxocyclohexylsulfonium and the like, and an onium salt of these cations with trifluoromethanesulfonate or nonafluorobutanesulfonate, Triphenylsulfonium trifluoromethanesulfonate or nonafluorobutanesulfonate of the formula (II) is preferred. These onium salts may be used alone or in combination of two or more.

In the present invention, the component (B) is
It is used in a proportion of 0.5 to 20 parts by mass, preferably 5 to 15 parts by mass, per 100 parts by mass of the component (A). If the amount of the component (B) is smaller than this, sufficient sensitivity cannot be obtained,
If the amount of the component (B) is larger than this, the depth of focus becomes narrower or the storage stability deteriorates.

Next, in the present invention, it is necessary to use a glycoluril in which the N-position is substituted with a hydroxyalkyl group or a lower alkoxyalkyl group or both, as the component (C), that is, the crosslinking agent. Such a crosslinking agent has a lower crosslinking ability than conventionally used alkoxymethylated melamine or alkoxymethylated urea. In the present invention, by utilizing such a low crosslinking ability, and combined with an onium salt, a skirting shape on the water-insoluble antireflection layer, a reduction in edge roughness or under the water-soluble antireflection layer. The cross-section of the T-shape was improved.

The crosslinking agent can be obtained by subjecting glycoluril and formalin to a condensation reaction, and by reacting the product with a lower alcohol. Such crosslinking agents include, for example, mono, di, tri or tetrahydroxymethyl glycoluril,
Di, tri or tetramethoxymethylated glycoluril, mono, di, tri or tetraethoxymethyl glycoluril, mono, di, tri or tetrapropoxymethylated glycoluril, mono, di, tri or tetrabutoxymethylated glycoluril, etc. is there. In addition, such a crosslinking agent can be obtained, for example, as a commercial product “N2702” (manufactured by Sanwa Chemical Co., Ltd.). These are mostly tri- and tetra-forms, and are mixtures of monomers, dimers and trimers.

The component (C) is blended in an amount of 3 to 50 parts by weight, preferably 10 to 20 parts by weight, based on 100 parts by weight of the component (A). If the amount is less than this range, the formation of crosslinks does not proceed, and a resist pattern cannot be obtained. If the amount is more than this range, storage stability and sensitivity of the resist coating solution are deteriorated with time, which is not preferable.

In the present invention, the above-mentioned component (A),
In addition to the component (B) and the component (C), an aliphatic lower amine of the component (D), an organic carboxylic acid of the component (E), or an oxo acid of phosphorus or a derivative thereof may be further contained, if desired. These are additional components commonly used in chemically amplified negative resists.

As the aliphatic lower amine of the component (D),
For example, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine,
Tertiary amines such as triethanolamine and tripropanolamine and secondary amines such as dipropylamine, dibutylamine, dipentylamine and dipropanolamine are preferred. The component (D) is used at a ratio of 0.01 to 1.0 part by mass per 100 parts by mass of the component (A).
As the organic carboxylic acid as the component (E), for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable. Further, as the oxo acid of phosphorus or a derivative thereof, phosphoric acid, a derivative such as phosphoric acid such as di-n-butyl phosphate, diphenyl phosphate, or a derivative thereof, phosphonic acid, dimethyl phosphonate, Acid-di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid such as dibenzyl ester and derivatives thereof such as esters, phosphinic acid,
Examples include phosphinic acids such as phenylphosphinic acid and derivatives such as esters thereof, among which phosphonic acid is particularly preferred. These components (E) are (A)
It is used at a ratio of 0.01 to 1.0 part by mass per 100 parts by mass of the component. These components (D) and (E) may be used alone or in combination.
Further, in the present invention, a surfactant for improving the resist coating property can be added as required.

In the present invention, a negative solution is prepared by using a coating solution prepared by dissolving the components (A) to (C) and the components (D) and (E) optionally used in an organic solvent. A mold resist layer is formed. The organic solvent used at this time may be any solvent that can dissolve each component,
There is no particular limitation. Examples of such solvents include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone and 2-heptanone, ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, Polyhydric alcohols such as dipropylene glycol or monomethyl ether of dipropylene glycol monoacetate, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and derivatives thereof, cyclic ethers such as dioxane, and methyl lactate , Ethyl lactate, methyl acetate,
Esters such as ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate can be mentioned. These may be used alone or as a mixture of two or more. In particular, considering the solubility of the components (B) and (C), a mixture of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate is preferred. The mass ratio of the mixture is preferably from 50:50 to 80:20.

In the light-sensitive material of the present invention, a water-insoluble antireflection layer is first formed on a substrate to a thickness of 30 to 300 nm. In the photosensitive material of the present invention, the thickness of the water-insoluble antireflection layer and the thickness of the negative resist layer provided thereon are important for obtaining a resist pattern having high resolution and excellent rectangularity. The thickness of the mold resist layer is 200 to
It is selected in the range of 500 nm, preferably 200 to 450 nm, more preferably 200 to 400 nm. Outside this range, a pattern having a fine pattern size and an excellent sectional shape cannot be obtained.

[0032]

Next, the present invention will be described in more detail by way of examples.

Example 1 A negative resist solution was prepared according to the following composition. (A) Component A copolymer of 80 mol% of hydroxystyrene having a mass average molecular weight of 2500 and 20 mol% of styrene 100 parts by mass (B) Component 3 parts by mass of triphenylsulfonium trifluoromethanesulfonate (C) Component Tetramethoxymethylated glycoluril ( 10 parts by mass (D) component 0.2 parts by mass of tributylamine (E) component 0.2 parts by mass of salicylic acid Others X-70- of fluorine / silicone surfactant 093 (manufactured by Shin-Etsu Chemical Co., Ltd.) 700 ppm based on the total solid content. That is, the components (A), (B), (C), (D) and (E) and the fluorosilicone-based surfactant were mixed with propylene glycol monomethyl ether 700 Parts by weight and 300 parts by weight of propylene glycol monomethyl ether acetate It was dissolved in objects, filtered through a pore size of 200nm membrane filter, to obtain a negative resist solution. On the other hand, a coating solution DUV-42 (manufactured by Brewer Science) on a 6-inch silicon wafer for forming an antireflection layer.
Was applied and dried, and then heated at 180 ° C. for 60 seconds to provide a water-insoluble antireflection layer having a thickness of 80 nm. The above negative resist solution was coated on the water-insoluble antireflection layer by 2500.
Spin coat at 30 rpm for 30 seconds and place on a hot plate 9
By drying at 0 ° C. for 60 seconds, a resist layer having a thickness of 500 nm was formed. Next, the reduced projection exposure apparatus FP
A-3000EX3 (manufactured by Canon Inc.) selectively irradiates a KrF excimer laser,
Post-heating treatment was performed for 0 second, followed by paddle development with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 60 seconds and rinsing with pure water for 15 seconds to obtain a negative resist pattern. The critical resolution of the resist pattern thus obtained is a line-and-space pattern of 180 nm, and the resist pattern has no rectangular skirt near the boundary with the anti-reflection layer, and has a rectangular shape that stands vertically from the plate surface. Was good. The minimum exposure (sensitivity) required to obtain a resist pattern of 180 nm was 40 mJ / cm ² . In addition, the line pattern had little edge roughness.

Example 2 In Example 1, the same amount of formula (B) was used as the component (B).

Embedded image A negative resist solution was prepared in the same manner as in Example 1, except that the compound represented by the formula (1) was used. Next, when patterning was performed in the same manner as in Example 1, the critical resolution of the obtained resist pattern was a line-and-space pattern of 180 nm, and the shape of the resist pattern was near the boundary with the water-insoluble antireflection layer. No scoring was observed, and a good rectangular shape stood vertically from the plate surface. The minimum exposure (sensitivity) required to obtain a resist pattern of 180 nm was 50 mJ / cm ² . In addition, the line pattern had little edge roughness.

Example 3 As the component (A) in Example 1, polyhydroxystyrene having a mass average molecular weight of 3000 in which 20% of the hydrogen atoms of the hydroxyl groups present therein were replaced by an isopropyl group which is an alkali-insoluble group was used. Except for the above, a negative resist solution was prepared in the same manner as in Example 1. Next, when patterning was performed in the same manner as in Example 1, the critical resolution of the obtained resist pattern was a line-and-space pattern of 180 nm, and the shape of the resist pattern was near the boundary with the water-insoluble antireflection layer. No scoring was observed, and a good rectangular shape stood vertically from the plate surface. The minimum exposure (sensitivity) required to obtain a resist pattern of 180 nm was 30 mJ / cm ² . In addition, the line pattern had little edge roughness.

Example 4 Example 1 was repeated except that the same amount of tetrabutoxymethylated glycoluril was used as the component (C) in Example 1.
In the same manner as in the above, a negative resist solution was prepared. Next, patterning was performed in the same manner as in Example 1. The resulting resist pattern had a critical resolution of 180 n.
m, and the resist pattern was good in the shape of a rectangle which stood vertically from the plate surface without any skirting near the boundary with the water-insoluble antireflection layer. The minimum exposure (sensitivity) required to obtain a resist pattern of 180 nm is 45 mJ.
/ Cm ² . In addition, the line pattern had little edge roughness.

Example 5 A negative resist solution was prepared according to the following composition. (A) Component A copolymer of 80 mol% of hydroxystyrene having a mass average molecular weight of 2500 and 20 mol% of styrene 100 parts by mass (B) Component 3 parts by mass of triphenylsulfonium trifluoromethanesulfonate (C) Component Tetramethoxymethylated glycoluril ( 10 parts by mass (D) component 0.2 parts by mass of tributylamine (E) component 0.2 parts by mass of salicylic acid Others X-70- of fluorine / silicone surfactant 093 (manufactured by Shin-Etsu Chemical Co., Ltd.) 700 ppm based on the total solids. That is, the components (A), (B), (C), (D) and (E) and the fluorosilicone surfactant were added to propylene glycol monomethyl ether 1050. Parts by mass and propylene glycol monomethyl ether acetate 450
After dissolving in a mixture of parts by mass, the solution was filtered through a membrane filter having a pore size of 200 nm to obtain a negative resist solution. On the other hand, an antireflection layer forming coating solution DUV-42 (manufactured by Brewer Science) is applied onto a 6-inch silicon wafer, dried, and then heated at 180 ° C. for 60 seconds to form a water-insoluble antireflection layer having a thickness of 80 nm. Provided. Apply the above negative resist solution on the water-insoluble antireflection layer
Spin coating at 500 rpm for 30 seconds and drying on a hot plate at 90 ° C. for 60 seconds to give a thickness of 300
A nm resist layer was formed. Then, K was reduced by a reduction projection exposure apparatus FPA-3000EX3 (manufactured by Canon Inc.).
After selective irradiation with rF excimer laser, 110
C. for 60 seconds, followed by paddle development with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 60 seconds and rinsing with pure water for 15 seconds.
A negative resist pattern was obtained. The critical resolution of the resist pattern thus obtained is a 150 nm line-and-space pattern, and the resist pattern shape has no skirting near the boundary with the water-insoluble antireflection layer and is perpendicular to the plate surface. The shape was good with a sharp rectangle. The minimum exposure (sensitivity) required to obtain a resist pattern of 150 nm was 40 mJ / cm ^2.
Met. In addition, the line pattern had little edge roughness.

Example 6 As the component (A) in Example 5, polyhydroxystyrene having a mass average molecular weight of 3000 in which 20% of the hydrogen atoms in the hydroxyl groups present therein were replaced by an isopropyl group which is an alkali-insoluble group was used. Except for the above, a negative resist solution was prepared in the same manner as in Example 5. Then, when patterning was performed in the same manner as in Example 5, the critical resolution of the obtained resist pattern was a 150 nm line-and-space pattern, and the resist pattern had a bottom near the boundary with the water-insoluble antireflection layer. No scoring was observed, and a good rectangular shape stood vertically from the plate surface. The minimum exposure (sensitivity) required to obtain a resist pattern of 150 nm was 35 mJ / cm ² . In addition, the line pattern had little edge roughness.

Example 7 Example 5 was repeated except that the same amount of tetrabutoxymethylated glycoluril was used as the component (C) in Example 5.
In the same manner as in the above, a negative resist solution was prepared. Next, when the patterning treatment was performed in the same manner as in Example 5, the critical resolution of the obtained resist pattern was 150 n.
m, and the resist pattern was good in the shape of a rectangle which stood vertically from the plate surface without any skirting near the boundary with the water-insoluble antireflection layer. The minimum exposure (sensitivity) required to obtain a resist pattern of 150 nm is 40 mJ.
/ Cm ² . In addition, the line pattern had little edge roughness.

Example 8 An antireflection layer forming coating solution DUV-42 (manufactured by Brewer Science) was applied on a 6-inch silicon wafer, dried, and then heated at 180 ° C. for 60 seconds to a thickness of 80 nm.
Was provided with a water-insoluble antireflection layer. Next, on this water-insoluble antireflection layer, the negative resist solution prepared in Example 5 was spin-coated at 2500 rpm for 30 seconds and dried on a hot plate at 90 ° C. for 60 seconds to form a resist layer having a thickness of 300 nm. Was formed. Next, a coating solution TSP-9 for forming a water-soluble antireflection layer is formed on the resist layer.
AEX (manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied and dried to a thickness of 42
nm of a water-soluble anti-reflection layer. Next, by a reduction projection exposure apparatus FPA-3000EX3 (manufactured by Canon Inc.),
After selective irradiation with KrF excimer laser, 11
Post-heat treatment at 0 ° C. for 60 seconds, then 2.38% by weight
A negative resist pattern was obtained by paddle development with an aqueous solution of tetramethylammonium hydroxide for 60 seconds and rinsing with pure water for 15 seconds. The critical resolution of the resist pattern thus obtained is a line-and-space pattern of 150 nm, and the resist pattern has no skirting near the boundary with the water-insoluble anti-reflection layer. The cross section of the interface with the layer did not become a T-shape, but a rectangle which stood vertically from the plate surface was shown. The minimum exposure (sensitivity) required to obtain a resist pattern of 150 nm was 40 mJ / cm ^2.
Met. In addition, the line pattern had little edge roughness.

Example 9 An antireflection layer forming coating solution DUV-42 (manufactured by Brewer Science) was applied to a 6-inch silicon wafer, dried, and then heated at 180 ° C. for 60 seconds to a thickness of 80 nm.
Was provided with a water-insoluble antireflection layer. On this water-insoluble anti-reflection layer, the negative resist solution of Example 1 was 2,500
Spin coat at 30 rpm for 30 seconds and place on a hot plate 9
By drying at 0 ° C. for 60 seconds, a resist layer having a thickness of 500 nm was formed. Then, a water-soluble anti-reflection layer forming coating solution TSP-9AEX (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied on the resist layer and dried to form a water-soluble anti-reflection layer having a thickness of 42 nm. Next, the reduced projection exposure apparatus FPA
After selectively irradiating a KrF excimer laser with -3000EX3 (manufactured by Canon Inc.),
A post-heating treatment was performed for seconds, followed by paddle development with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 60 seconds and rinsing with pure water for 15 seconds to obtain a negative resist pattern. The critical resolution of the resist pattern thus obtained is a line-and-space pattern of 180 nm, and the resist pattern has no skirting near the boundary with the water-insoluble antireflection layer. The cross section of the interface with the layer was not a T-shape, but was a rectangular shape that stood perpendicular to the plate surface. The minimum exposure (sensitivity) required to obtain a resist pattern of 180 nm was 40 mJ / cm ² . In addition, the line pattern had little edge roughness.

Comparative Example 1 5 parts by mass of tris (2,3-dibromopropyl) isocyanurate as the component (B) in Example 1 and (C)
Methoxymethylated urea (manufactured by Sanwa Chemical Co., Ltd.)
A negative resist solution was prepared in the same manner as in Example 1 except that 10 parts by mass of the product name “Mx290”) was used.
Next, patterning was performed in the same manner as in Example 1, and the resulting resist pattern had a critical resolution of 20.
It was a line-and-space pattern of 0 nm, and the resist pattern had a skirt near the boundary with the water-insoluble antireflection layer. The minimum exposure (sensitivity) required to obtain a resist pattern of 200 nm is 10
It was 0 mJ / cm ² .

Comparative Example 2 A negative resist solution was prepared in the same manner as in Example 1 except that 5 parts by mass of tris (2,3-dibromopropyl) isocyanurate was used as the component (B) in Example 1. . Next, patterning was performed in the same manner as in Example 1, but a resist pattern could not be formed.

Comparative Example 3 Example 5 was repeated except that 5 parts by mass of bis (cyclohexylsulfonyl) diazomethane was used as the component (B) in Example 1.
In the same manner as in Example 1, a negative resist solution was prepared. Then, when patterning was performed in the same manner as in Example 1, the critical resolution of the obtained resist pattern was a line-and-space pattern of 300 nm, and the shape of the resist pattern was near the boundary with the water-insoluble antireflection layer. Grinding was observed. The minimum exposure (sensitivity) required to obtain a 300 nm resist pattern was 50 mJ / cm ² .

Example 10 Instead of the silicon wafer provided with the water-insoluble antireflection layer in Example 1, a silicon wafer provided with a SiON film (inorganic antireflection film) by a CVD method was used. A negative resist pattern was formed in the same manner as in Example 1 except that the film thickness was changed to 450 nm.
The critical resolution of the resist pattern thus obtained is a 180 nm line and space pattern,
The shape of the resist pattern did not show any skirting near the boundary with the antireflection layer, and was a good rectangular shape which stood vertically from the substrate. The minimum exposure (sensitivity) required to obtain a resist pattern of 180 nm is 40 m.
J / cm ² . In addition, the line pattern had little edge roughness.

[0046]

According to the present invention, a two-layered multilayer photosensitive material comprising a negative resist layer and a water-insoluble antireflection layer or a negative resist layer, a water-insoluble antireflection layer and a water-soluble antireflection layer are provided. In the three-layered multi-layer photosensitive material of the present invention, there can be provided an advantage that a resist pattern having good rectangularity can be provided without generating a skirt or a T-shaped cross section.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/3415 C08K 5/3415 5/42 5/42 5/521 5/521 C08L 101/14 C08L 101 / 14 G03F 7/004 501 G03F 7/004 501 501 503 503A 7/11 503 7/11 503 H01L 21/027 H01L 21/30 502R (72) Inventor Naotaka Kubota 150 Nakamaruko Nakahara-ku Kawasaki City, Kanagawa Prefecture Higashikyo Ohka Kogyo Inside (72) Inventor Miwa Miyairi 150 Nakamaruko, Nakahara-ku, Kawasaki City, Kanagawa Prefecture Inside Tokyo Ohka Kogyo Co., Ltd. In-house (72) Inventor Kotaro Endo 150 Nakamaruko, Nakahara-ku, Kawasaki City, Kanagawa Prefecture

Claims (6)

[Claims] A water-insoluble antireflection layer having a thickness of 30 to 300 nm is provided on a substrate, and a 200 to 500 nm thickness is formed thereon.
A multilayer photosensitive material provided with a negative resist layer of
The negative resist layer comprises (A) an alkali-soluble resin,
(B) an onium salt that generates an acid upon irradiation with radiation and (C) at least one cross-linking group selected from a hydroxyalkyl group and a lower alkoxyalkyl group.
The glycoluril substituted at the position is converted to the component (A) 100
A photosensitive material containing 0.5 to 20 parts by mass of the component (B) and 3 to 50 parts by mass of the component (C) per part by mass. 2. The light-sensitive material according to claim 1, wherein the water-insoluble antireflection layer contains an acid component. 3. The photosensitive material according to claim 1, further comprising a water-soluble antireflection layer provided on the negative resist layer. 4. The light-sensitive material according to claim 3, wherein the water-soluble antireflection layer contains a water-soluble resin component and a fluoroalkyl sulfonate or a fluoroalkyl carboxylate. 5. The negative resist layer further comprises (D) an aliphatic lower amine in an amount of 0.01 to 100 parts by mass per component (A).
5. The light-sensitive material according to claim 1, wherein the light-sensitive material is contained in a ratio of 1.0 part by mass. 6. The negative resist layer further comprises (E) an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof in a proportion of 0.01 to 1.0 part by mass per 100 parts by mass of the component (A). 6. The photosensitive material according to any one of 1 to 5.