JPH0519479A - Positive type photosensitive composition and photosensitive laminate formed by using the composition - Google Patents

Abstract

PURPOSE:To provide the positive type photosensitive resin compsn. which is excellent in performance, such as photosensitivity, stability and development latitude, and can form resist patterns having a high resolution and the photosensitive laminate formed by using this compsn. CONSTITUTION:This positive type photosensitive resin compsn. has the tetrahydropyranyl ester structure of carboxylic acid in the molecule and a compd. which forms an acid when irradiated with active rays. The above- mentioned photosensitive laminate is constituted by laminating the layer of this compsn. on a base material. This photosensitive resin compsn. has the excellent solubility in org. solvents and compotability with other resins and is excellent in the performance, such as photosensitivity, stability and development latitude and can form the resist patterns having the high resolution.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive resin composition capable of forming a fine resist pattern suitable for manufacturing semiconductor devices, magnetic bubble memories, electronic parts such as integrated circuits, lithographic printing plates and the like. The present invention relates to an article and a photosensitive laminate using the same.

[0002]

2. Description of the Related Art Conventionally, an orthoquinonediazide compound has been mainly used as a photosensitive material for forming a positive resist pattern used for manufacturing electronic parts, printing plates and the like. However, the orthoquinonediazide compound has a drawback of low photosensitivity because it has a quantum yield of at most 1 and is difficult to sensitize. In addition, since the photosensitive wavelength is fixed, there is a problem in that it cannot follow the shortening of the exposure wavelength for the purpose of improving the resolution of the photoresist.

Therefore, in recent years, a positive combination of a compound which produces an acid upon irradiation with light and a compound which undergoes a reaction such as decomposition by an acid and is solubilized in a developing solution, mainly for the purpose of improving sensitivity and resolution. Type photosensitive system has been attracting attention.

As an example of this, a combination of a compound capable of generating an acid upon irradiation with light and an acetal compound (Japanese Patent Application Laid-Open No. 48-48).
89003), in combination with a polymer having an acetal group or a ketal group in the main chain (JP-A-53-1334).
29), a combination with an enol ether compound (JP-A-55-12995), and a polymer having an orthoester group in the main chain (JP-A-56-1734).
5), and a polymer having a tert-butyl ester of a carboxylic acid or a tert-butyl carbonate group of a phenol (JP-A-2-27660).
And so on. However, these are
It was not always satisfactory in terms of photosensitivity, stability, development latitude, etc.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a positive type photosensitive resin composition which is excellent in performance such as photosensitivity, stability and development margin and which can form a high resolution resist pattern. And

[0006]

The present invention has solved the above problems by combining a compound having a tetrahydropyranyl ester structure of a carboxylic acid with a compound which produces an acid upon irradiation with light.

That is, the present invention provides a positive photosensitive resin composition containing a compound having a tetrahydropyranyl ester structure of a carboxylic acid in the molecule and a compound capable of generating an acid upon irradiation with an actinic ray, and a substrate. The present invention relates to a photosensitive laminated body formed by laminating layers of the photosensitive resin composition.

The present invention will be described in detail below. In the present invention, the “tetrahydropyranyl ester structure of carboxylic acid” has the formula

[Chemical 3] Means a structure represented by. This structure improves the solubility of the composition in a general-purpose organic solvent and the compatibility with other resins. The compound having a tetrahydropyranyl ester structure of carboxylic acid in the molecule can be obtained by the series of operations described below. A compound having a carboxyl group in the molecule and 2,3-dihydro-4H-pyran are dissolved in a suitable solvent such as ethyl acetate, and a catalytic amount of acid such as hydrochloric acid is added,
Heat to ~ 80 ° C. The target compound can be obtained in about 6 hours to 10 days.

In the present invention, the compound having the tetrahydropyranyl ester structure of carboxylic acid in the molecule is a compound having one or more tetrahydropyranyl ester structure of carboxylic acid in one molecule,
There is no particular limitation. The following are some specific examples of compounds having a tetrahydropyranyl ester structure of a carboxylic acid in the molecule that can be used in the present invention. In the structural formula below, T
HP represents a tetrahydropyranyl group.

In the case of low molecular weight compounds, the following compounds may be mentioned, for example.

[Chemical 4]

[Chemical 5]

Examples of the polymer compound include homopolymers of the following monomers and copolymers of the following monomers with other copolymerizable monomers.

[Chemical 6]

Among these, a homopolymer of tetrahydropyranyl acrylate or tetrahydropyranyl methacrylate, a copolymer of tetrahydropyranyl acrylate or tetrahydropyranyl methacrylate and another copolymerizable monomer, and the like are preferable.

Examples of the other monomer here include methyl methacrylate, ethyl methacrylate, n
-Butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, 2-
Examples thereof include hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylonitrile, styrene, α-methylstyrene, diacetone acrylamide, vinyltoluene and the like, and these can be used alone or in combination of two or more kinds for copolymerization. However, the copolymerization amount of these other copolymerizable monomers is preferably 80 parts by weight or less based on 100 parts by weight of the total amount of all the monomers constituting the copolymer. If this amount exceeds 80 parts by weight,
Light sensitivity tends to be low.

The homopolymer or copolymer is synthesized by mixing the polymerizable monomer in an organic solvent with 2,2'-azobis (isobutyronitrile) or 2,2'-azobis (2,4-dimethylvaleronitrile). ) Or other azo compound-based or benzoyl peroxide-based peroxide-based polymerization initiator. As the organic solvent used at this time, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanol, butyl acetate, chlorobenzene, dioxane or the like is used. To be

The weight average molecular weight (in terms of polystyrene) of the homopolymer or copolymer is preferably in the range of 5,000 to 150,000. This weight average molecular weight is 500
If it is less than 0, the mechanical strength of the resist is weak and it is 150,000.
When it exceeds, the viscosity of the solution becomes high and it becomes difficult to obtain a thin uniform coating film (photosensitive film).

When a low molecular weight compound is used among the compounds having a tetrahydropyranyl ester structure of carboxylic acid in the molecule, it is necessary to use a binder together from the viewpoint of film-forming property. The binder here is a polymer used for improving the film-forming property, and is preferably a homopolymer or copolymer of the above-mentioned monomer having a tetrahydropyranyl ester structure of carboxylic acid in the molecule. .
Examples of other binders are water or aqueous base soluble polymers such as phenol novolac resins, cresol novolac resins, melamine-formaldehyde resins,
Polyethylene oxide, polyacrylamide, poly-P
-Vinylphenol, polymethacrylic acid, and the like. The amount of these binders used is preferably 80 parts by weight or less based on 100 parts by weight of the total amount of the low molecular weight compound having a tetrahydropyranyl ester structure of carboxylic acid in the molecule and the binder. If it exceeds 80 parts by weight, the photosensitivity is lowered. Of course, if the binder is a homopolymer or copolymer of a monomer having a tetrahydropyranyl ester structure of carboxylic acid in the molecule, it may exceed 80 parts by weight.

On the other hand, when the compound having a tetrahydropyranyl ester structure of a carboxylic acid in the molecule is a homopolymer or a copolymer, no binder may be used, but it is soluble in the above-mentioned water or aqueous base. 5% of the total 100 parts by weight of the polymer of homopolymer or copolymer and binder.
You may use it by 0 weight part or less. If it exceeds 50 parts by weight,
Compatibility may decrease.

The amount of the compound having the tetrahydropyranyl ester structure of carboxylic acid in the molecule is 100 weight% of the total amount of the compound having the tetrahydropyranyl ester structure of carboxylic acid in the molecule and the compound which produces an acid by irradiation with actinic rays. The content is preferably 50 to 99.5 parts by weight, more preferably 70 to 98 parts by weight. Fifty
If it is less than 1 part by weight, the content of the compound that produces an acid upon irradiation with actinic rays is too high, and the stability tends to decrease. If it exceeds 99.5 parts by weight, the photosensitivity decreases.

Next, as typical examples of compounds which generate an acid upon irradiation with actinic rays,

[Chemical 7] An oxadiazole derivative substituted with a trihalomethyl group such as

[Chemical 8] An s-triazine derivative substituted with a trihalomethyl group such as

[Chemical 9] Iodonium salts such as

[Chemical 10] Sulfonium salts such as

[Chemical 11] A disulfone derivative such as

[Chemical 12] And imidosulfonate derivatives thereof.

In particular, the following general formula (I) or (II)

[Chemical 13] A nitrobenzyl derivative represented by is preferable. Here, R represents an alkyl group, and is an alkyl group having 1 to 4 carbon atoms, for example, methyl group, ethyl group, n-propyl group, n
It is preferable to represent a -butyl group or the like.

Typical examples of the compounds represented by the above general formulas (I) and (II) include the following compounds.

[Chemical 14]

[Chemical 15]

The amount of the compound which forms an acid upon irradiation with actinic rays is 100 parts by weight in total of the compound having a tetrahydropyranyl ester structure of a carboxylic acid in the molecule and the compound which forms an acid upon irradiation with actinic rays. Of these, 0.5 to 50 parts by weight is preferable, and 2 to 3
More preferably, it is 0 part by weight. If it is less than 0.5 part by weight, the photosensitivity is low, and if it exceeds 50 parts by weight, the stability tends to decrease.

A sensitizer may be further added to the positive photosensitive resin composition of the present invention. Examples of sensitizers that can be used include perylene, pyrene, anthracene, thioxanthone, Michler's ketone, benzophenone, 9-fluorenone and anthrone.
The amount of these sensitizers to be used is preferably in the range of 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the compound that produces an acid upon irradiation with actinic rays. If it is less than 1 part by weight, the sensitizing effect is small,
If it exceeds 100 parts by weight, the sensitizer tends to be insoluble or precipitated.

The positive type photosensitive resin composition of the present invention may further contain a paint, a pigment, a plasticizer, a surface smoothness imparting agent, an adhesion promoter, an inorganic filler and the like.

The positive-type photosensitive resin composition of the present invention is usually a solution of each of the above components dissolved in an organic solvent, and the solution is applied onto a substrate and dried to form a photosensitive film on the substrate. It can be formed into a photosensitive laminate. After that, an actinic ray is imagewise irradiated, preferably after-heating is performed, and then the exposed portion is removed by a developing solution by development to form a resist pattern.

Examples of the organic solvent for dissolving the positive photosensitive resin composition of the present invention include methyl ethyl ketone, dioxane, cyclohexanone, toluene, 1-methoxy-2-propanol, ethyl lactate, 1-methoxy-2-.
Propyl acetate, ethylene dichloride, butyl acetate and the like can be mentioned. These organic solvents may be used alone or 2
You may use together more than one kind. Generally, the positive photosensitive resin composition of the present invention is dissolved in these organic solvents in an amount of 1 to 50% by weight and used. If the concentration is less than 1% by weight, it is difficult to uniformly form a photosensitive film, and if it exceeds 50% by weight, it is difficult to form a thin photosensitive film.

The base material on which this solution is applied to form the photosensitive film is aluminum, zinc,
Metal plate such as iron, plastic film such as polyethylene, polycarbonate, cellulose acetate, polyvinyl acetal, plastic film or paper laminated with metal foil, metal-deposited plastic film or paper, copper clad laminate, silicon wafer, dioxide A typical example is a silicon wafer.

Examples of the method of applying the solution of the positive type photosensitive resin composition onto these substrates include spin coating, spraying, solution casting, dip coating and the like. In this way, the photosensitive film may be formed directly on the substrate used,
In addition, a photosensitive film is previously formed on a support film such as a plastic film typified by a polyester film, the film is laminated on a target substrate, and the photosensitive film is formed on the surface of the target substrate. Can also be formed.
The film pressure of the photosensitive film varies depending on the use, but is usually 0.1 to 1
The range is 00 μm.

Examples of the light source of actinic rays for irradiating the obtained photosensitive film on an image include a mercury lamp, a xenon lamp,
High density energy beam such as metal halide lamp, chemical lamp, carbon arc lamp, g-line, i-line, deep-UV light, helium neon laser, argon ion laser, krypton ion laser, helium / cadmium ion laser, KrF excimer laser. Can also be used.

After irradiation with actinic rays, in order to accelerate the decomposition of the tetrahydropyranyl ester structure, the temperature is 60 to 160 ° C.
It is preferable to heat in the range of 0.5 to 30 minutes.

The developer used for developing the positive photosensitive resin composition of the present invention is an inorganic alkali such as sodium metasilicate, sodium carbonate, sodium hydroxide or potassium hydroxide or an organic alkali such as tetraalkylammonium salt. Aqueous solutions are preferred. The concentration of the alkaline aqueous solution is preferably 0.1 to 15% by weight, and 0.5 to
It is more preferably 5% by weight. If it is less than 0.1% by weight, it is difficult to completely remove the exposed portion in a short time, and if it exceeds 15% by weight, the unexposed portion may be partially damaged. The developing method is carried out by spraying the above developing solution or immersing it in the developing solution.

[0032]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these.

Example 1 Cresol novolac resin (meta / para ratio = 40/6
0, weight average molecular weight 8500) 14 g, terephthalic acid ditetrahydropyranyl ester 6 g, the above general formula (I)
P-nitrobenzyl derivative in which R in the formula is an ethyl group.
A solution obtained by mixing 3 g and 80 g of dioxane was applied on a silicon wafer by a spin coater and dried at 100 ° C. for 15 minutes to form a photosensitive film having a film thickness of 2 μm. The surface of this photosensitive film is passed through a photomask with a 40 kW ultra-high pressure mercury lamp.
Light exposure of 0 mJ / cm ² and 10 at 140 ° C
After post-heating for a minute, spray development was performed with a 1 wt% sodium metasilicate aqueous solution, and as a result, a good resist pattern with a resolution of 3 μm was formed.

Example 2 90 g of dioxane was placed in a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas introducing tube, stirred, and heated to a temperature of 90 ° C. while blowing nitrogen gas. When the temperature became constant at 90 ° C., a solution obtained by mixing 90 g of tetrahydropyranyl acrylate and 0.9 g of 2,2′-azobis (isobutyronitrile) was dropped into the flask over 2 hours, and then 4 The temperature was maintained at 90 ° C. for a while with stirring. After 4 hours, a solution prepared by dissolving 0.42 g of 2,2'-azobis (2,4-dimethylvaleronitrile) in 20 g of dioxane was added dropwise to the flask over 10 minutes, and then the mixture was kept warm at 90 ° C for 5 hours with stirring. did.

The homopolymer of tetrahydropyranyl acrylate thus obtained (weight average molecular weight 350
00g) solution 40 g (polymer solid content 18 g), a solution obtained by adding 2 g of a p-nitrobenzyl derivative in which R in the general formula (I) is an n-butyl group and 58 g of methyl ethyl ketone is applied onto a silicon wafer by a spin coater. Then 10
It was dried at 0 ° C. for 15 minutes to form a photosensitive film having a film thickness of 2 μm.
The surface of this photosensitive film was exposed to a light amount of 200 mJ / cm ² with a super-high pressure mercury lamp of 3 kW through a photomask, and after heating at 145 ° C. for 10 minutes, spray development was performed with a 1 wt% sodium metasilicate aqueous solution. As a result, a good resist pattern having a resolution of 2 μm was formed.

Example 3 90 g of 1-methoxy-2-propanol was placed in a flask equipped with the same apparatus as in Example 2, stirred, and heated to a temperature of 90 ° C. while blowing nitrogen gas. Temperature is 90 ℃
When the temperature became constant, 45 g of tetrahydropyranyl acrylate, 45 g of methyl methacrylate and 2,2 '
A liquid in which 0.9 g of azobis (isobutyronitrile) was mixed was dropped into the flask over 2 hours, and then, the temperature was kept stirring at 90 ° C. for 4 hours. After 4 hours 2,2'-
Azobis (2,4-dimethylvaleronitrile) 0.4g
A solution of 20 g of 1-methoxy-2-propanol was added dropwise into the flask over 10 minutes, and then 90 ° C again.
It was kept warm while stirring for 5 hours.

The tetrahydropyranyl acrylate copolymer thus obtained (weight average molecular weight 3800
0) solution 40 g (polymer solid content 18 g), p-nitrobenzyl derivative 2 g in which R in the general formula (I) is an n-butyl group, and methyl ethyl ketone / dioxane = 1 /
A solution containing 58 g of 1 (weight ratio) of a mixed solvent was applied on a silicon wafer by a spin coater, and the solution was applied at 100 ° C. for 15
After minute drying, a photosensitive film having a film thickness of 4 μm was formed. The surface of this photosensitive film was exposed through a photomask with an ultrahigh pressure mercury lamp of 3 kW at a light amount of 400 mJ / cm ² , and after heating at 130 ° C. for 20 minutes, spray development was performed with a 1 wt% sodium metasilicate aqueous solution. As a result, a good resist pattern having a resolution of 8 μm was formed.

Example 4 36 g of polymer solution obtained in Example 2 (polymer solid content 16
g), terephthalic acid ditetrohydropyranyl ester 4
1.0 g of a p-nitrobenzyl derivative in which R in the general formula (I) is an n-butyl group, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine A solution containing 6 g and 60 g of dioxane was applied on a silicon wafer by a spin coater and dried at 100 ° C. for 15 minutes to form a photosensitive film having a film thickness of 0.5 μm. The surface of this photosensitive film was exposed through a photomask with an ultrahigh-pressure mercury lamp of 3 kW at a light amount of 300 mJ / cm ² , and further 1
After post-heating at 40 ° C. for 5 minutes, spray development was performed with a 1 wt% sodium carbonate aqueous solution. As a result, a good resist pattern with a resolution of 1 μm was formed.

[0039]

The positive photosensitive resin composition of the present invention has excellent solubility in general-purpose organic solvents and compatibility with other resins, high photosensitivity, and good stability and development latitude. Is. By using the positive photosensitive resin composition of the present invention, a high resolution resist pattern can be obtained.

Claims (4)

[Claims] 1. A positive type photosensitive resin composition comprising a compound having a tetrahydropyranyl ester structure of a carboxylic acid in the molecule and a compound capable of generating an acid upon irradiation with an actinic ray. 2. A compound having a tetrahydropyranyl ester structure of a carboxylic acid in the molecule is a homopolymer of tetrahydropyranyl acrylate / or tetrahydropyranyl methacrylate or tetrahydropyranyl acrylate / or tetrahydropyranyl methacrylate and another polymerizable monomer. The positive photosensitive resin composition according to claim 1, which is a copolymer of 3. A compound which forms an acid upon irradiation with actinic rays is represented by the general formula (I): [Wherein R represents an alkyl group] or a compound represented by the general formula (II): The positive photosensitive resin composition according to claim 1 or 2, which is a compound represented by the formula: wherein R represents the above substance. 4. A laminate comprising a substrate and a layer of the photosensitive resin composition according to claim 1, 2 or 3 laminated on the substrate.