JPH08160634A - Resist developer composition - Google Patents

Abstract

(57) [Summary] [Structure] A polyhydric alcohol is blended in a proportion of 20 to 50% by weight based on the total amount of the composition, with respect to a resist developer containing an organic base containing no metal ions as a main component. A developer composition for a resist. [Effect] It has an excellent anticorrosion effect on a metal substrate, does not have an adverse effect such as peeling of the upper metal film even on a substrate on which different kinds of metals are laminated, and has a good developability. It is preferably used in manufacturing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel resist developer composition, more specifically, an excellent anticorrosive action on a metal substrate,
The present invention relates to a resist developer composition which is suitable for use in the field of manufacturing semiconductor devices, liquid crystal display devices, and the like, since it has no peeling of the upper metal film and has good developability.

[0002]

2. Description of the Related Art Conventionally, in the manufacture of semiconductor elements, liquid crystal display elements, etc., ultraviolet rays and deep ultraviolet rays are used for the purpose of selectively protecting the underlying substrate before performing etching or diffusion treatment on the underlying substrate. A resist sensitive to actinic radiation such as excimer laser, X-ray, and electron beam is applied on the substrate, dried, and a resist film is formed, followed by selective irradiation of actinic radiation and development to form a resist pattern on the substrate. The so-called lithographic method is generally used.

In such a lithographic method, when an alkaline aqueous solution is used as a developing solution, a developing solution generally containing no metal ions, for example, tetramethyl, is used so as not to adversely affect electric characteristics of a semiconductor element, a liquid crystal display element and the like. Ammonium Hydroxide ["IBM Technical Disclosure Bulletin (IBM Tech
natural Disclosure Bulleti
n) "Volume 3, Issue 7, 2009 (1970)
Year)], or trimethyl (2-hydroxyethyl)
Ammonium hydroxide (U.S. Pat. No. 4,239,661)
An aqueous solution containing an organic base as a main component is used.

Further, for the purpose of improving the developability, a developing solution prepared by mixing various additives into the above-mentioned aqueous solution containing an organic base as a main component, for example, a specific quaternary ammonium compound is contained as a surfactant. Developer (JP-A-58-91)
No. 43), 0.2-3.5% by weight of tetramethylammonium hydroxide and 0.2-10 of polyhydric alcohol.
Developer consisting of an aqueous solution containing 50% by weight (JP-A-64-
No. 19344) is also known. Such a developer containing an aqueous solution containing an organic base as a main component is easy to store and treat as a waste liquid and has no flammability. Therefore, there is a tendency that the demand as a versatile developer increases.

By the way, as a substrate used in the manufacture of semiconductor elements and liquid crystal display elements, a silicon wafer or a glass plate provided with a metal film such as aluminum for forming an electrode circuit is used. When a metal film pattern is formed on a substrate by a lithographic method using a substrate on which a metal film is formed, with a conventional developer,
There is a drawback that the metal film is easily corroded. In addition, a substrate which has been attracting attention as a display element of a thin film transistor (TFT) in recent years is such that a transparent conductive film such as an indium oxide film or an ITO film made of an oxide of indium and tin is formed on a glass plate, and an aluminum film is formed on the transparent conductive film. In many cases, a vapor deposition film is provided, but when a pattern of an aluminum film is formed by a lithographic method using a substrate formed by laminating such dissimilar metals, the conventional developer may peel off the aluminum film, Alternatively, there is a defect that a gas is generated at the interface between aluminum and the transparent conductive film thereunder, and the gas pushes up the aluminum to explode, and improvement thereof is strongly demanded.

[0006]

Under the circumstances described above, the present invention has an excellent anticorrosion action especially for metal substrates.
Even in a substrate on which dissimilar metals are laminated, there is no adverse effect such as peeling of the upper metal film, and the developability is good, and it is a resist developer suitable for use in the production of semiconductor elements, liquid crystal display elements, etc. It was made for the purpose of providing a composition.

[0007]

The inventors of the present invention have conducted extensive studies to develop a resist developer composition that does not adversely affect a metal substrate. It was found that the object can be achieved by adding a polyhydric alcohol in a specific ratio to a resist developing solution containing an organic base as a main component, and the present invention has been completed based on this finding. .

That is, according to the present invention, the polyhydric alcohol is added in an amount of 20 to 50% by weight based on the total amount of the composition in the resist developing solution containing an organic base containing no metal ions as a main component.
The present invention provides a resist developer composition characterized by being blended at a ratio of.

The organic base containing no metal ion used in the composition of the present invention includes, for example, amines having a linear, branched or cyclic primary, secondary or tertiary amine substituent. Specifically, diaminoalkanes such as 1,3-diaminopropane, arylamines such as 4,4′-diaminodiphenylamine, alkylamines such as N, N′-diaminodialkylamine, and 3 to 5 carbon atoms in the ring skeleton. A heterocyclic base having one atom and one or two heteroatoms selected from nitrogen, oxygen and sulfur, such as pyrrole, pyrrolidine, pyrrolidone, pyridine, morpholine, pyrazine, piperidine, oxazole and thiazole. Can be mentioned. Also, lower alkyl quaternary ammonium salts and the like are used. Specific examples thereof include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, triethyl (2-hydroxyethyl) ammonium hydroxide, tripropyl (2-hydroxy). Examples thereof include ethyl) ammonium hydroxide and trimethyl (1-hydroxypropyl) ammonium hydroxide. Of these organic bases, lower alkyl quaternary ammonium salts, especially tetramethylammonium hydroxide, are preferred. These organic bases are
Each of these may be used alone or in combination of two or more.

The appropriate concentration of each of these organic bases is selected depending on the type of organic base used and the resist, but is usually 2.0 to 10 based on the total amount of the composition.
The concentration is adjusted to a concentration of 3.5% by weight, preferably 3.5 to 7.0%. If the concentration is less than 2.0% by weight, development cannot be sufficiently performed and a resist pattern is hard to be formed, which is not preferable. If it exceeds 10% by weight, in the case of a positive type resist, the film loss of the unexposed portion becomes large, and it is difficult to form a good resist pattern, which is not preferable.

In the composition of the present invention, a polyhydric alcohol is blended with a developer comprising an aqueous solution containing an organic base containing no metal ion as a main component. Examples of the polyhydric alcohol include glycerin and propylene. Glycol, ethylene glycol and the like can be mentioned. Particularly, glycerin can be preferably used because of its excellent anticorrosion effect even in a small amount. These polyhydric alcohols may be used alone or in combination of two or more, and the amount of the polyhydric alcohol to be blended is from an aqueous solution containing an organic base containing no metal ion as a main component. It is added in a proportion of 20 to 50% by weight based on the total amount of the composition with respect to the developing solution. If the content is less than 20% by weight, no practical anticorrosive effect can be obtained, and if it exceeds 50% by weight, the positive resist has a large film loss in the unexposed portion and a good resist pattern cannot be formed.

The composition of the present invention contains various additives commonly used in conventional resist developing solutions, such as surfactants, lubricants, wetting agents, etc., within a range not impairing the object of the present invention.
You may add a stabilizer, a dissolution aid, etc. suitably.

The composition of the present invention has an excellent anticorrosion effect and can form a high quality metal film pattern on a substrate having a metal film formed thereon without corroding the metal film. , Copper, tantalum, an alloy of aluminum and copper, etc. are used. Further, the composition of the present invention is a substrate on which different kinds of metals are laminated, for example, an IT film including an oxide film of indium or an oxide of indium and tin.
It is also effective for a substrate in which a vapor-deposited aluminum film is formed on a transparent conductive film such as an O film, and does not peel or rupture the aluminum film.

Further, as the resist targeted by the composition of the present invention, any resist can be used regardless of whether it is a negative type or a positive type, as long as it can be developed using an aqueous alkaline solution. it can. Specifically, a positive resist containing a naphthoquinonediazide compound and a novolak resin, a positive resist containing a compound that generates an acid upon exposure and a compound that is decomposed by the acid to increase the solubility in an aqueous alkaline solution and an alkali-soluble resin. Resist,
A positive resist containing a compound that generates an acid upon exposure and an alkali-soluble resin having a group that is decomposed by the acid to increase the solubility in an alkaline aqueous solution, and a crosslinking reaction is initiated by the compound that generates an acid upon exposure and the acid. A negative resist containing a cross-linking agent and an alkali-soluble resin may be used.

[0015]

Since the resist developer composition of the present invention has excellent anticorrosion properties, it suppresses corrosion of the metal film during development of the resist provided on the metal film, and also dissimilar metals are laminated. Even for the substrate, the metal in the upper layer will not be peeled off or ruptured, so it is necessary to manufacture semiconductor elements, liquid crystal display elements, etc. in which formation of fine electrode circuits is indispensable, or a substrate on which different metals are laminated. It can be used particularly effectively in the manufacture of the TFT display element used.

[0016]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Tetramethylammonium hydroxide 3.5% by weight
And a developing solution consisting of an aqueous solution containing 20% by weight of glycerin were prepared, and aluminum was vapor-deposited in a thickness of 1,000Å on the surface of a glass plate of 2 × 3 cm in the developing solution (200 ml, 23 ° C). The substrate thus obtained was dipped and allowed to stand still, and the time until the aluminum was corroded and completely dissolved was measured.

On the surface of a 2 × 3 cm glass plate,
An ITO film composed of an oxide of indium and tin was formed, and a substrate obtained by vapor-depositing aluminum with a film thickness of 400 Å on the ITO film was placed in a developing solution (200 ml, 23 ° C).
After immersing for 10 minutes and standing still, the surface condition of aluminum was observed, and when peeling of aluminum from the ITO film was observed, x was evaluated, and when peeling was not observed, it was evaluated as ◯. Table 1 shows the results.

Examples 2 to 8 and Comparative Examples 1 to 3 Tetramethylammonium hydroxide and polyhydric alcohols of the types shown in Table 1 were prepared and implemented as an aqueous solution containing the polyhydric alcohols at the concentrations shown in Table 1. The test was conducted in the same manner as in Example 1. The results are shown in Table 1.

[0020]

[Table 1]

[Note] TMAH: tetramethylammonium hydroxide G: glycerin EG: ethylene glycol PG: propylene glycol

EXAMPLE 9 100 parts by weight of cresol novolac resin and 2,3,4 of naphthoquinone-1,2-diazide-5-sulfonic acid
A positive resist solution was prepared by dissolving 30 parts by weight of trihydroxybenzophenone ester in 390 parts by weight of ethylene glycol monoethyl ether acetate, and filtering the resulting solution using a 0.2 μm membrane filter.

Next, this positive resist solution was applied onto a 4-inch silicon wafer on which aluminum was vapor-deposited.
Apply with a spinner and 110 ° C on a hot plate,
After forming a resist film having a thickness of 1.35 μm by drying for 90 seconds, the reduction projection exposure apparatus NSR-1505G
4D (manufactured by Nikon Corporation) was used to perform exposure through a test chart mask. Next, a stationary paddle type developing device was used to perform a developing treatment at a temperature of 23 ° C. for 65 seconds using the same developing solution as in Example 2, followed by a rinse treatment with pure water for 30 seconds and then drying. As a result of observing the surface state of the obtained resist pattern and the exposed aluminum, a resist pattern having a good shape was formed, the exposed aluminum was not discolored, and no corrosion portion was observed.

Comparative Example 4 Except that the developer used in Comparative Example 2 was used,
As a result of observing the obtained resist pattern and the state of exposed aluminum in the same manner as in Example 9, although a resist pattern having a good shape was obtained, the aluminum was discolored and corrosion was observed.

Claims (4)

[Claims] 1. A resist characterized in that a polyhydric alcohol is blended in a proportion of 20 to 50% by weight based on the total amount of the composition in a resist developing solution containing an organic base as a main component which does not contain metal ions. Developer composition. 2. An organic base containing no metal ions,
Tetramethylammonium hydroxide 2.0-10
The resist developer composition according to claim 1, which is contained at a concentration of wt%. 3. The resist developer composition according to claim 1, wherein the polyhydric alcohol is at least one selected from glycerin, propylene glycol and ethylene glycol. 4. The resist developer composition according to claim 3, wherein the polyhydric alcohol is glycerin.