JP2626068B2 - Photoresist composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a photoresist composition. More specifically, the present invention relates to a photoresist composition particularly preferably used for forming a fine pattern on a high-reflectance substrate such as aluminum in the manufacture of semiconductor devices such as ICs and LSIs.

<Prior Art> Conventionally, in the manufacture of integrated circuits such as LSIs, a photoresist made of a quinonediazide-based photosensitive agent and a novolak-based resin, and a photoresist made of a bisazide-based photosensitive agent and a cyclized rubber-based resin have been used.

In the manufacture of integrated circuits, a fine pattern is formed using a photoresist on various substrates, but on a high-reflectivity substrate such as aluminum, aluminum-silicon, and polysilicon, the conventional photoresist does not have a substrate surface or steps. Unnecessary areas are exposed to light due to reflection of light on the side surfaces, and cause problems such as so-called notching and halation.

In order to improve the above problem and prevent the resolution from decreasing, Japanese Patent Publication No. Sho 51-37562 discloses the following formula having an absorption characteristic in the ultraviolet region. A photoresist composition containing a dye (oil yellow [CI-11020]) as a light absorbing agent has been proposed. Accordingly, light transmitted through the photoresist layer can be sharply reduced, and light sneak into the light-shielding region can be reduced.

Hereinafter, in the present invention, for example, a composition comprising a resin such as a novolak-based resin and a photosensitizer is referred to as a “photoresist”, and a composition containing a light absorbing agent is referred to as a “photoresist composition”. .

In general, the addition of a light-absorbing agent greatly reduces the sensitivity of the photoresist, and causes an undesired problem in that the productivity in manufacturing semiconductors is reduced.

Usually, a method of forming a resist film is to apply a photoresist composition containing a solvent to a wafer and pre-bake to remove the solvent.However, some light-absorbing agents precipitate during storage or sublimate during pre-bake. As a result, there is a problem that the concentration is lowered and the resist performance varies.

<Problems to be Solved by the Invention> The inventors of the present invention have made intensive studies to overcome the above-mentioned disadvantages of the prior art, and as a result, have completed the present invention.

That is, an object of the present invention is to eliminate the drawbacks of the prior art and form a high-resolution pattern on a high-reflectivity substrate that is free from halation and notching, and that is stable against pre-baking. It is another object of the present invention to provide a highly sensitive photoresist composition in which a decrease in sensitivity due to addition of a light absorbing agent is small.

Another object of the present invention is to include a light absorbing agent having good compatibility with the photoresist, and the light absorbing agent is contained in the photoresist composition during storage or in the photoresist composition film after coating and pre-baking. An object of the present invention is to provide a photoresist composition for fine processing that does not precipitate on the surface.

<Means for Solving the Problems> As a result of intensive studies, the present inventors have found that the use of the compound of the general formula (I) as a light-absorbing agent can alleviate the drawbacks of the prior art at a glance. The invention has been completed.

That is, the present invention provides a compound represented by the general formula (I): (Where R is hydrogen, an alkyl group having 1 to 5 carbon atoms, 1 carbon atom
Represents an alkoxy group, a hydroxy group, a halogen atom, or a nitro group. A photoresist composition comprising the compound of the present invention.

Compounds of general formula (I) are described in Inorg. Chem. 26, 4312-4318.
(1987). That is, the formula (I
It can be synthesized by a condensation reaction between the compound of the formula (I) and the compound of the formula (III).

(In the formula, R has the same meaning as described above.) Examples of the compound of the general formula (I) include the compounds in Table 1, and the like, but the present invention is not limited thereto. Can be used as a mixture of two or more.

As a photoresist serving as a base material of the photoresist composition used in the present invention, for example, a photoresist composed of a novolak resin obtained by addition condensation of phenols and formaldehyde and a naphthoquinonediazide compound is suitably used. Among them, m-cresol and / or p
-Cresol novolak resin synthesized from cresol and formalin or m-, p-cresol and cresol-based novolak resin synthesized from 3,5-xylenol and formalin and 2,3,4-trihydroxybenzophenone, 2,3, 4,4'-tetrahydroxybenzophenone, 2,
2 ', 4,4'-tetrahydroxybenzophenone, 2,3,
3 ', 4-tetrahydroxybenzophenone, 2,2', 3,4,5
-Pentahydroxybenzophenone, 2,3,3 ', 4,5-pentahydroxybenzophenone, 2,3,3', 4,4'-pentahydroxybenzophenone, 2,2'3,4,4'-pentahydroxybenzophenone A photoresist containing naphthoquinone-1,2-diazidosulfonic acid ester of a polyhydroxybenzophenone such as 2,2 ', 3,3', 4-pentahydroxybenzophenone is preferably used.

General formula (I) in the photoresist composition of the present invention
The amount of the compound represented by is usually 0.1 to 20%, more preferably 0.2 to 10%, based on the solid content of the photoresist. If the amount is too small, the effect of preventing halation is small, and if it is too large, the profile and sensitivity tend to deteriorate. In the composition of the present invention, one or more other compounds can be used in combination with the compound of the present invention.

Among these compounds of the present invention, especially 550 nm or less,
More preferably, a compound having an absorption maximum for light in the region of 300 to 450 nm is preferably used.

<Effects of the Invention> According to the present invention, the disadvantages of the prior art are eliminated at once, and a high-resolution pattern without halation or notching can be stably formed on a high-reflectivity substrate without lowering productivity. Its industrial utility value is immeasurable, as it can be formed.

<Examples> Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Examples 1-2 and Comparative Examples 1-2 Positive photoresist PF-6200 containing a novolak resin and at least one o-quinonediazide compound (trade name, manufactured by Sumitomo Chemical Co., Ltd., solid content ratio: 31.0 wt%) )
Each compound shown in Table 2 was added to prepare a photoresist composition. However, in Comparative Example 2, the positive photoresist PF-6200 was used as it was. The compounds of Examples 1 and 2 were synthesized by the method described above. The amount of each compound added was such that the absorbance of the photoresist composition at 365 nm was the same as that of Comparative Example 1 (1.0 wt% of the compound relative to the solid content of the photoresist).

These photoresist compositions were spin-coated on a 4-inch silicon wafer with an aluminum film with a spinner so as to have a thickness of 1.8 μm, and prebaked at 100 ° C. for 1 minute on a hot plate. This was exposed using a reduction projection exposure apparatus (exposure wavelength i-line: 365 nm) with a stepwise changing exposure amount via a test reticle. Furthermore, SOPD
(Developer for positive resist, trade name, manufactured by Sumitomo Chemical Co., Ltd.) was used and developed by an automatic developing machine by a stationary paddle method at 23 ° C. for 60 seconds.

Table 2 shows the evaluation results of the obtained resist patterns. In this table, the relative sensitivity is a ratio when the amount of exposure necessary for resolving the resist film of Comparative Example 2 is 1, and the absorbance ratio is the absorbance of the photoresist composition of Comparative Example 1 at 365 nm. Is a ratio when 1 is set to 1. Also,
The antihalation effect was evaluated by the following method.

[Evaluation method of halation prevention effect]

1. Production of Stepped Substrate for Evaluation A stepped pattern having the shape shown in FIG. 1 was formed on a silicon substrate having a 1 μm thick SiO ₂ film by photolithography, etching and aluminum sputtering. Typical pattern sizes are a = 4 μm, b =
2 μm, c = 1 μm, and d = 1 μm.

2. Evaluation of antihalation effect A 1.8 μm-thick resist film is formed by spin coating on the high-reflectivity stepped substrate prepared by the above method. The line width (x) of the portion having no step shown in FIG. 2 is 1.2 μm across the central concave portion of the step pattern shown in FIG.
Exposure and development are performed so that m resist lines are formed. The line width (y) of the resist remaining at the center of the stepped recess after the exposure and development was measured, and the reduction ratio of y to x [R = (x−
y) / x].

When the reduction rate (R) of the line width is within 10%, the halation prevention effect is determined to be “excellent”, and when it is 11 to 20%, it is determined to be “good”.
21% or more are judged as "bad".

As shown in Table 2, in the example, a pattern was formed with high sensitivity. It was found that the formed pattern was sharply resolved, had no notch due to reflected light on the side surface of the pattern, and was excellent in the effect of preventing halation from the aluminum surface.

On the other hand, the photoresist of the comparative example was insufficient in sensitivity or antihalation effect.

[Brief description of the drawings]

FIG. 1 is an evaluation step pattern shape diagram. FIG. 2 is a view in which a photoresist is applied, exposed, and developed.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Yasunori Uetani 3-1-1, Kasuganaka, Konohana-ku, Osaka-shi, Japan Within Sumitomo Chemical Industries Co., Ltd. (72) Takanori Yamamoto Kasuga, Konohana-ku, Osaka-shi, Osaka Naka 3-chome No. 98 Sumitomo Chemical Co., Ltd. (56) References JP-A-53-70817 (JP, A) JP-A-55-77741 (JP, A)

Claims (1)

(57) [Claims] 1. The compound of the general formula (I) (Where R is hydrogen, an alkyl group having 1 to 5 carbon atoms, 1 carbon atom
Represents an alkoxy group, a hydroxy group, a halogen atom, or a nitro group. A photoresist composition comprising the compound of the above).