JPH05173319A - Composition for photoresist - Google Patents

Abstract

PURPOSE:To obtain a compsn. for a photoresist useful for photoresist patterning in the production of a semiconductor device, an integrated circuit, and an offset printing plate, etc. CONSTITUTION:Fine powder of a metal oxide or metal oxyhydroxide having 0.002-0.2mum average particle diameter is incorporated into a photosensitive resin such as novolak resin by 0.05-20wt.% to obtain the objective compsn. for a photoresist.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoresist composition useful for processing a photoresist pattern in the production of semiconductor elements, integrated circuit structures, and offset printing plate making.

[0002]

TECHNICAL BACKGROUND AND PROBLEMS OF THE INVENTION In the field of electronics industry, precision processing of element elements such as transistors and capacitors constituting a semiconductor integrated circuit and so-called printed circuit boards such as wiring connecting them are used for fine circuit systems. At the time of precision processing, a technique of photolithography, in which a resist pattern serving as an etching mold is photopatterned on a substrate to be processed, has become widespread. However, high integration of semiconductor devices brings advantages such as low price, high performance, high reliability, and high functionality, and thus technological development for higher integration is required. The photoresist for precision microfabrication is required to have high performance in various characteristics. In particular, a material having high etching resistance in a so-called wet type or dry type is required. For this reason, various proposals have been made to improve the etching resistance of the photosensitive resin base.

The inventors of the present invention have long conducted various studies on the addition of metal oxides such as titanium oxide and titanium oxyhydroxide or powders of oxymetal hydroxides as a functional material to increase the added value or to form a composite material. However, as a result of further research focusing on improving the functionality of photoresists for microfabrication by metal oxides and oxymetal hydroxides in the process, titanium oxide fine powder with specific properties was identified as photoresists. As a result, the inventors have found that they can further improve etching resistance without deteriorating the photosensitivity, and have completed the present invention.

[0004]

The present invention relates to the photoresist composition shown below. (1) Photoresist composition comprising fine powder of metal oxide or oxymetal hydroxide having an average particle diameter of 0.002 to 0.2 μm in an amount of 0.05 to 20% by weight based on the photosensitive resin. The photoresist composition according to item (1), wherein the compound, (2) the metal oxide is titanium dioxide, and (3) the photosensitive resin is a novolac resin. It is a composition for use.

Various kinds of metal oxides and oxymetal hydroxides can be used in the photoresist composition of the present invention. Examples thereof include titanium dioxide, titanium oxyhydroxide [TiO (OH) ₂ ], and oxidation. Examples thereof include silicon, aluminum oxide, aluminum oxyhydroxide, iron oxide, ferric tetroxide (magnetite), iron oxyhydroxide, zinc oxide, and magnesium oxide. However, these are, for example, in the case of fine powder of titanium dioxide or titanium oxyhydroxide, fine titanium oxyhydroxide obtained by heating or hydrolyzing a titanium sulfate solution or titanium tetrachloride solution, Alternatively, fine powder of titanium dioxide or titanium oxyhydroxide made of anatase type crystal or rutile type crystal such as those obtained by firing or pulverizing this, or gas phase oxidative decomposition of titanium tetrachloride, or a mixture thereof, or, for example, The fine powder of silicon oxide is obtained by vapor-phase hydrolysis of silicon tetrachloride, or silicon oxide obtained by decomposing a sodium silicate solution with an acid or an ammonium salt, followed by firing and crushing. The fine powder of metal oxide or oxymetal hydroxide of these powders has an average particle size of about 0.002 to 0.2 μm, and Preferably one having a uniform Konado distribution in about 0.01~0.05μm. If the average particle diameter is larger than the above range, it is not possible to form a highly precise fine pattern with high resolution. If the average particle size is smaller than the above range, fine particles of metal oxides or oxymetal hydroxides in the coating solution tend to induce secondary agglomeration in the process of forming a resist layer on the substrate, which is not preferable. ..

In the present invention, various photosensitive resin bases for positive resists and negative resists can be used as the photosensitive resin base constituting the photoresist composition. For positive resist, for example, phenol or cresol-based novolac resin-based quinonediazide-based, photosensitive polymethacrylic resin-based, and for negative-type resist, for example, cyclized rubber or phenolic resin-based azide-based, photosensitive polyimide-based. , Polyvinyl cinnamate type, and the like. In the present invention,
The amount of fine powder of metal oxide or oxymetal hydroxide constituting the photoresist composition is 0.05 to 20% by weight, preferably 0.1 to 10% by weight, based on the photosensitive resin.
Is. If the added amount is less than the above range, the desired effect cannot be obtained, and if it is more than the above range, a highly precise fine pattern cannot be formed.

[0007]

【Example】

Example 1 A sodium hydroxide solution was added to a titanium tetrachloride solution for partial neutralization, and then the temperature was raised and a sodium hydroxide solution was further added under heating to be neutralized to obtain a titanium dioxide hydrate oxide and filtered. After washing, the wet cake is baked and crushed to have an average particle size of 0.
Titanium dioxide fine powder having a rutile type crystal of 015 μm (specific surface area 85 m ² / g) was obtained. Using the titanium dioxide fine powder thus obtained, a photosensitive resin coating composition having the following composition was prepared. Titanium dioxide fine powder 5 parts by weight Novolac resin 100 〃 quinonediazide 15 〃 ethyl cellosolve acetate 20 〃 The obtained coating solution was applied on an aluminum vapor-deposited polyester film and a silicon wafer substrate by a spin coater and then dried. A resist film was formed. Step exposure on the resist film under the wedge 1
Xenon mercury lamp (HOYA HLS
-200 type) and exposed for 60 seconds. Then, development was performed using a developing solution (composition: 1% KOH aqueous solution). The exposure sensitivity characteristic [mJ (millijoule) / cm ² ] of the resist film was evaluated from the developability with respect to each step exposure wedge. Thereafter, the developed resist film was subjected to 1305 MH under an O ₂ gas partial pressure of 20 mToor (millitorr).
Etching treatment was performed for 10 minutes with a high frequency plasma of Z (discharge power 50 W). The resist film thickness after etching was measured (stylus method) and the etching resistance was evaluated from the remaining thickness ratio. The results are shown in Table 1.

Example 2 Silicon tetrachloride was hydrolyzed in a flame of oxygen and hydrogen to obtain silicon dioxide fine powder (specific surface area 200 m ² / g) having an average particle diameter of 0.012 μm. Using the silicon oxide fine powder thus obtained, a resist film was prepared by treating in the same manner as in Example 1, and then the exposure sensitivity characteristics and etching resistance were evaluated. The results are shown in Table 1.

Comparative Example In the example, the same process as in the example was carried out except that the resist film was formed without using the titanium dioxide fine powder. The exposure sensitivity characteristics and etching resistance of this resist film are shown in Table 1.

[0010]

[Table 1]

[0011]

The photoresist composition of the present invention can improve the etching resistance without deteriorating the photosensitivity and can further increase the added value as the photoresist composition.

Claims (3)

[Claims] 1. A photoresist comprising fine powder of metal oxide or oxymetal hydroxide having an average particle diameter of 0.002 to 0.2 μm in an amount of 0.05 to 20% by weight with respect to a photosensitive resin. Composition. 2. The photoresist composition according to claim 1, wherein the metal oxide is titanium dioxide. 3. The photoresist composition according to claim 1, wherein the photosensitive resin is a novolac resin.