JPH0990631A - Negative resist composition and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the sensitivity and resolution and to improve adhesiveness to a substrate and stability against time lapse without being affected by oxygen by incorporating a hydroxypropyl cellulose and a photo-acid initiator as essential components. SOLUTION: This negative resist composition contains the hydroxypropyl cellulose and the photo-acid initiator, and after a photosensitive layer is formed, it is exposed to radiation and heat-treated to allow the photo-acid initiator to generate an acid, resulting in cross-linking the hydroxypropylcellulose and insolubilizing it to form a negative pattern. The hydroxy-propylcellulose is produced by allowing propylene oxide to react with cellulose and it has a fundamental structure represented by the formula and a substitution rate of hydroxyl group for hydroxypropyl group is, usually, 53.4-77.5%. The photo-acid initiator is a compound to generate an acid by irradiation with radiation, such as light, and it is exemplified by bis(trihalomethyl)-1,3,5-triazine derivatives, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative resist composition and a pattern forming method using the same, and in particular, a negative resist composition having good adhesion to a substrate and capable of high sensitivity and high resolution water development. The present invention relates to an object and a negative pattern forming method using the same.

[0002]

2. Description of the Related Art Conventionally, photolithography, short wavelength ultraviolet (deep UV) lithography, electron beam (EB)
As a resist material used for various kinds of lithography such as lithography and X-ray lithography, various positive type and negative type materials are known.

Among them, as a water-developable negative pattern-forming photosensitive resin (resist material), natural proteins such as gelatin and casein or polyvinyl alcohol to which a dichromate is added are known. There is. However, in this case, since the dichromate is used, there are problems that various problems of environmental pollution are caused and that stability with time is poor.

Further, as disclosed in JP-B-56-5761, JP-B-56-5762, and JP-A-56-11906, a styrylpyridinium or styrylquinolinium type photosensitive group is used. A resist material using a pendant photosensitive polyvinyl alcohol is known. In this case, the storage stability is good and the sensitivity is high, but there is a problem that the resolution and the adhesion to the substrate are not good.

There is also a resist material using a water-soluble bisazide compound and polyvinylpyrrolidone or a copolymer of acrylamide and diacetone acrylamide. In this case, the sensitivity is high, the storage stability is good, and the resolution is quite good, but the adhesion to the substrate is not good and the resolution is also insufficient.

Further, when polyvinyl alcohol and a diazonium salt are used, there is a problem that the resolution and the adhesion are good, but the stability with time and the sensitivity are not good.

On the other hand, when a water-developable photopolymerizable resist material is used, it may have a high sensitivity, but may be affected by the inhibition of oxygen polymerization. Therefore, in order to prevent this, a protective film for preventing oxygen is required, which complicates the manufacturing process and lowers the resolution.

[0008]

Therefore, at present, there is a demand for a resist material having high sensitivity, high resolution, good adhesion to a substrate, no influence of oxygen, and good stability over time. ing.

In view of such circumstances, the present invention provides a resist composition having high sensitivity, high resolution, good adhesion to a substrate, no influence of oxygen, and good stability over time. An object is to provide a pattern forming method using the same.

[0010]

A first aspect of the present invention for achieving the above object is a negative resist composition containing hydroxypropyl cellulose and a photo-acid generator as essential components. .

A second aspect of the present invention is the negative resist composition according to the first aspect, wherein the unexposed portion of the photosensitive layer formed using the composition can be removed with water.

A third aspect of the present invention is the photoacid generator according to the first or second aspect, wherein the photoacid generator is an organic solvent-soluble halogen-containing triazine or halogen-containing oxadiazole. A negative resist composition is characterized in that hydroxypropyl cellulose is dissolved in an organic solvent.

A fourth aspect of the present invention is the first, second or third aspect.
In the above embodiment, there is further provided a negative resist composition in which a phosphor, an inorganic powder or an organic powder is dispersed.

A fifth aspect of the present invention is any one of the first to fourth aspects, further containing at least one selected from the group consisting of a cross-linking agent having an N-methylol structure and a polyfunctional epoxy compound. And a negative resist composition.

A sixth aspect of the present invention is a step of forming a photosensitive layer by applying a negative resist composition containing hydroxypropyl cellulose and a photo-acid generator as essential components to a substrate and drying the composition. A negative pattern forming method is characterized by including a step of imagewise exposing the photosensitive layer, a step of heat-treating the imagewise exposed photosensitive layer, and a step of developing the heat-treated photosensitive layer with water.

In a seventh aspect of the present invention based on the sixth aspect, the negative resist composition contains an organic solvent-soluble halogen-containing triazine or halogen-containing oxadiazole as a photo-acid generator. The method for forming a negative pattern is characterized in that the acid generator and the hydroxypropyl cellulose are dissolved in an organic solvent.

An eighth aspect of the present invention is the negative resist composition according to the sixth or seventh aspect, further comprising:
A pattern forming method is characterized in that a phosphor, an inorganic powder or an organic powder is dispersed.

In a ninth aspect of the present invention according to any one of the sixth to eighth aspects, the negative resist composition further comprises a cross-linking agent having an N-methylol structure and a polyfunctional epoxy compound. The negative pattern forming method is characterized by containing at least one selected.

The negative resist composition of the present invention has hydroxypropyl cellulose and a photo-acid generator, and when exposed (radiated) after the photosensitive layer is formed and heat-treated, hydroxypropyl cellulose is generated by the acid generated from the photo-acid generator. Are believed to crosslink and become insoluble to form a negative pattern.

The negative resist composition of the present invention has high sensitivity and high resolution, has good adhesion to the substrate, is not affected by oxygen, and has good stability over time.

Further, in the composition in which the phosphor, the inorganic powder, or the organic powder is dispersed, the phosphor pattern, the insulating film pattern made of the inorganic powder, and the organic powder pattern are formed and then baked. Since the property is good, the pattern is fused in the film, and it is possible to form a pattern having good water resistance and chemical resistance.

In JP-A-6-342212, a polymer compound containing a cellulose skeleton containing hydroxypropyl cellulose in the main chain and the main chain being cleaved by an acid, and an acid generated when irradiated with radiation are disclosed. Disclosed is a resist for forming a fine pattern containing an acid generator for producing a positive-type pattern, in which a polymer compound of the cellulose skeleton is reduced in molecular weight by an acid, and a positive pattern is obtained. Is completely different.

The hydroxypropyl cellulose used in the present invention is produced by reacting cellulose with propylene oxide and has a basic structure represented by the following structural formula.

[0024]

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Here, the substitution ratio of the hydroxyl group to the hydroxypropyl group is usually 53.4 to 77.5%.

The photoacid generator which can be used in the present invention is a compound which generates an acid when irradiated with radiation such as light (exposure), and is bis (trihalomethyl) -1,3,5.
-Halogenated organic compounds such as triazine derivatives and 2-halomethyl-1,3,4-oxadiazole derivatives; onium acids such as triphenylsulfonium salts, diphenyliodonium salts and phenyldiazonium salts; 1,2
-Naphthoquinonediazide-4-sulfonyl chloride,
Examples thereof include sulfonic acid derivatives such as 1,2-naphthoquinonediazide-4-sulfonic acid ester, nitrobenzyl sulfonate compound, aryl sulfonic acid ester, and imino sulfonate.

It is preferable to use a photoacid generator soluble in an organic solvent, particularly a halogen-containing triazine or a halogen-containing oxadiazole. Thereby, the photo-acid generator and the hydroxypropyl cellulose can be dissolved in an organic solvent to obtain a negative resist composition.

The negative resist composition of the present invention may further contain a phosphor, an inorganic powder or an organic powder dispersed therein. Here, the one containing the phosphor is, for example,
It is for forming a pattern for a fluorescent display tube, a color cathode ray tube, and a plasma display. In addition, those containing organic powder are, for example, liquid crystal display devices and CCDs.
For forming the color filter pattern. Furthermore, as the inorganic powder, those containing hard glass powder and ceramic powder can form an insulating layer,
Further, those containing powders of iron oxide (FeO ₃ ), chromium oxide (CrO ₃ ), copper oxide (CuO), etc. can form an insulating pattern having light-shielding performance, while gold,
Those containing a powder of silver, copper or the like can form a conductive pattern.

The negative resist composition of the present invention may further contain at least one selected from the group consisting of a crosslinking agent having an N-methylol structure and a polyfunctional epoxy compound. When the crosslinking agent having a N-methylol structure or the polyfunctional epoxy compound is contained, the water resistance of the cured film is improved, and the sensitivity is improved.

Examples of the cross-linking agent having an N-methylol structure include methylolated urea, methylolated alkyl carbamate, methylolated melamine, methylolated guanamine, and alkyl ethers thereof.

Examples of polyfunctional epoxy compounds include sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, glycerol triglycidyl ether, trimethylolpropane polyglycidyl ether, and polyethylene glycol diglycidyl ether.

In the negative resist composition of the present invention, each component is preferably dissolved in an organic solvent as described above. Here, as the organic solvent that can be used in the present invention, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether. Acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, 2-methoxyethyl acetate,
2-ethoxyethyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, 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, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate , Ethyl hydroxyacetate, 2-
Methyl hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutylbutyrate, ethyl acetate, Butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethyl An acetamide etc. can be mentioned.

Further, the negative resist composition of the present invention may contain various additives as required. For example, a water-soluble diluent having a hydroxyl group such as ethylene glycol, propylene glycol, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and sorbitol, or various surfactants, adhesion aids, storage stabilizers and the like can be contained.

The mixing ratio of the negative resist composition of the present invention is not limited as long as it does not deviate from the object of the present invention, but generally 1 to 50 parts by weight of a photo-acid generator is added to 100 parts by weight of hydroxypropyl cellulose. , Preferably 4 to 20
Parts by weight.

When the phosphor or the inorganic powder is contained, 1 part is added to 100 parts by weight of a photosensitive composition containing hydroxypropyl cellulose and a photoacid generator.
The amount is 00 to 5000 parts by weight, preferably 200 to 3000 parts by weight. Furthermore, when containing an organic powder,
The amount is 10 to 500 parts by weight, preferably 20 to 200 parts by weight, based on 100 parts by weight of the photosensitive composition.

The negative resist composition of the present invention can be applied to a substrate and dried to form a photosensitive layer. Further, the photosensitive layer thus formed is exposed to an image and heat-treated to render the exposed portion water-insoluble,
A negative pattern can be formed by developing this with water.

Here, the method for forming the photosensitive layer, the image exposure method, the heat treatment method and the like are not particularly limited as long as they are generally performed by those skilled in the art. The heat treatment after image exposure is usually 30 to 200 ° C, preferably 40 to 150 ° C.

[0038]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples, but these Examples do not limit the scope of the present invention in any way.

Example 1 First, a photosensitive solution (resist composition) having the following composition was prepared.

Hydroxypropyl cellulose 10 parts by weight (Nippon Soda Co., Ltd .: HPC-M) 1 part by weight of a photoacid generator having the following structural formula (Sanwa Chemical Co., Ltd .: TFE-triazine) Phosphor 100 parts by weight Propylene glycol 600 parts by weight of monomethyl ether

[0041]

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The photosensitive solution was applied onto an indium tin oxide (ITO) substrate with a spin coater and dried at 70 ° C. for 10 minutes to form a photosensitive layer containing a phosphor and having a thickness of 10 μm.

Next, after exposing at 200 mj / cm ² with an ultrahigh pressure mercury lamp through a mask having a dot pattern, it was heated at 100 ° C. for 7 minutes. Then, it was developed with spray water to obtain a 40 μm square phosphor pattern.

Example 2 First, a photosensitive solution (resist composition) having the following composition was prepared.

Hydroxypropyl cellulose 10 parts by weight (manufactured by Nippon Soda Co., Ltd .: HPC-M) 1 part by weight of the photo-acid generator used in Example 1 (manufactured by Sanwa Chemical Co., Ltd .: TFE-triazine) methylated melamine resin 1 .6 parts by weight Hydroxymethyl methacrylate 1.4 parts by weight Phosphor 100 parts by weight Propylene glycol monomethyl ether 600 parts by weight

The photosensitive solution was applied onto an indium tin oxide (ITO) substrate with a spin coater and dried at 70 ° C. for 10 minutes to form a photosensitive layer containing a phosphor and having a thickness of 10 μm.

Next, after exposing at 100 mj / cm ² with an ultrahigh pressure mercury lamp through a mask having a dot pattern, it was heated at 100 ° C. for 7 minutes. Then, it was developed with spray water to obtain a 40 μm square phosphor pattern.

Example 3 First, a photosensitive solution (resist composition) having the following composition was prepared.

Hydroxypropyl cellulose 100 parts by weight (Nippon Soda Co., Ltd .: HPC-M) Photoacid generator having the following structural formula 10 parts by weight (Sanwa Chemical Co., Ltd .: TME-triazine) Propylene glycol monomethyl ether 330 parts by weight

[0050]

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The photosensitive solution was applied onto an indium tin oxide (ITO) substrate with a spin coater and dried at 70 ° C. for 10 minutes to form a photosensitive layer having a thickness of 2.2 μm.

Then, through a mask having a line-and-space pattern (L / S), an ultra-high pressure mercury lamp is used for 30 times.
After performing mj / cm2 exposure, it was heated at 80 ° C. for 5 minutes. Then, develop with water to obtain a clean L / of 20 μm.
An S pattern was obtained.

Example 4 First, a photosensitive solution (resist composition) having the following composition was prepared.

Hydroxypropyl cellulose 100 parts by weight (Nippon Soda Co., Ltd .: HPC-M) Photoacid generator used in Example 3 10 parts by weight (Sanwa Chemical Co., Ltd .: TME-triazine) Glycerol triglycidyl ether 20 Parts by weight (Nagase Kasei Co., Ltd .: Denacol EX-314) Propylene glycol monomethyl ether 330 parts by weight

The photosensitive solution was applied onto an indium tin oxide (ITO) substrate and dried in the same manner as in Example 3 to form a photosensitive layer having a thickness of 2.2 μm.

Then, using a mask having a line-and-space pattern (L / S), an ultra-high pressure mercury lamp is used for 20 times.
After performing mj / cm2 exposure, it was heated at 90 ° C. for 3 minutes. Then, develop with water to obtain a clean L / of 20 μm.
An S pattern was obtained.

Example 5 First, a photosensitive solution (resist composition) having the following composition was prepared.

Hydroxypropylcellulose 100 parts by weight (Nippon Soda Co., Ltd .: HPC-M) Photoacid generator used in Example 3 10 parts by weight (Sanwa Chemical Co., Ltd .: TME-triazine) Methylated melamine resin 15 Parts by weight (Mitsui Cyanamid: Cymel 301) Propylene glycol monomethyl ether 330 parts by weight

The photosensitive solution was applied onto an indium tin oxide (ITO) substrate and dried in the same manner as in Example 3 to form a photosensitive layer having a thickness of 2.2 μm.

Then, using a mask having a line-and-space pattern (L / S), an ultra-high pressure mercury lamp is used for 20 times.
After performing mj / cm2 exposure, it was heated at 100 ° C. for 7 minutes. Then, by water development, clean L / of 20 μm
An S pattern was obtained.

Example 6 First, a photosensitive solution (resist composition) having the following composition was prepared.

Hydroxypropylcellulose 100 parts by weight (Nippon Soda Co., Ltd .: HPC-M) Photoacid generator having the following structural formula 10 parts by weight Methylated melamine resin 15 parts by weight (Mitsui Cyanamid: Cymel 301) 2 -Hydroxypropyl methacrylate 14 parts by weight Propylene glycol monomethyl ether 330 parts by weight

[0063]

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In the same manner as in Example 3, such a photosensitive solution was applied onto an indium tin oxide (ITO) substrate and dried at 50 ° C. for 5 minutes to form a photosensitive layer having a thickness of 2.2 μm.

Then, using a mask having a line-and-space pattern (L / S), an ultra-high pressure mercury lamp is used for 20 times.
After performing mj / cm ² exposure, it was heated at 70 ° C. for 5 minutes. Then, develop with water for 2 minutes, and clean L / of 20 μm
An S pattern was obtained.

(Example 7) As shown in the table below, a photosensitive solution was prepared by adding TFE-triazine in an amount of 4 to 20 parts by weight to 100 parts by weight of the above-mentioned HPC-M. Then, each was applied onto a glass substrate and then dried at 70 ° C. for 10 minutes to form a photosensitive layer having a thickness of 1 μm. 15 mj / cm2 for each photosensitive layer
After exposure, each of them was heated as shown in the following table. Next, after water-development of each, the patterns were observed with a microscope. As a result, a 20 μm L / S pattern was clearly resolved in each case.

[0067]

[Table 1]

Example 8 The following resist composition was prepared.

Hydroxypropylcellulose 10 parts by weight (Nippon Soda Co., Ltd .: HPC-M) 1,2-naphthoquinonediazide-4-sulfonyl chloride 1 part by weight Methylated melamine resin 1.6 parts by weight (manufactured by Sanwa Chemical Co., Ltd.) : Nicalac MW-30) Hydroxyethyl methacrylate 1.4 parts by weight Propylene glycol monomethyl ether 350 parts by weight

A resist layer having a thickness of 1.0 μm was formed by applying and drying the resist composition on an alkali glass substrate in the same manner as in Example 3. Then, 1.0 mj / cm ² with an ultra-high pressure mercury lamp through a mask having L / S.
And then heated at 80 ° C. for 5 minutes. afterwards,
After water development for 2 minutes, a clear 20 μmL / S pattern was obtained.

[0071]

According to the present invention, by using hydroxypropyl cellulose and a photoacid generator, high sensitivity,
It is possible to provide a resist composition having a high resolution, good adhesion to a substrate, being not affected by oxygen, and having good stability over time, and a pattern forming method using the resist composition.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location H01L 21/027 H01L 21/30 502R 569F

Claims (9)

[Claims] 1. A negative resist composition comprising hydroxypropyl cellulose and a photo-acid generator as essential components. 2. The negative resist composition as claimed in claim 1, wherein the unexposed portion of the photosensitive layer formed by using the composition can be removed with water. 3. The photoacid generator according to claim 1 or 2, wherein the organic solvent-soluble halogen-containing triazine or halogen-containing oxadiazole is used, and the photoacid generator and the hydroxypropylcellulose are dissolved in an organic solvent. And a negative resist composition. 4. The negative resist composition according to claim 1, further comprising a phosphor, an inorganic powder or an organic powder dispersed therein. 5. The negative resist according to claim 1, further comprising at least one selected from the group consisting of a cross-linking agent having an N-methylol structure and a polyfunctional epoxy compound. Composition. 6. A step of forming a photosensitive layer by coating a negative resist composition containing hydroxypropyl cellulose and a photo-acid generator as essential components on a substrate and drying, and exposing the photosensitive layer to image exposure. A negative pattern forming method comprising: a step, a step of heat-treating the image-exposed photosensitive layer, and a step of developing the heat-treated photosensitive layer with water. 7. The negative resist composition according to claim 6, wherein the organic acid-soluble halogen-containing triazine or halogen-containing oxadiazole is contained as the photo-acid generator, and the photo-acid generator and the hydroxypropyl cellulose are contained. Is dissolved in an organic solvent, a negative pattern forming method. 8. The pattern forming method according to claim 6, wherein the negative resist composition further contains a phosphor, an inorganic powder or an organic powder dispersed therein. 9. The negative resist composition according to claim 6, further comprising at least one selected from the group consisting of a cross-linking agent having an N-methylol structure and a polyfunctional epoxy compound. And a negative pattern forming method.