JPH04134350A - Rinse liquid for photosensitive polyimide - Google Patents

Abstract

PURPOSE:To surely prevent the temp. fall of the rinse liquid and the generation of scum, etc., occurring therein and to eliminate the possibility of ignition by using 1 to 6C primary alcohol as the rinse liquid for photosensitive polyimide. CONSTITUTION:The rinse liquid to be used in a rinse stage for removing a developer in a developing stage for the photosensitive polyimide is constituted of 1 to 6C primary alcohol. As 1 to 6C primary alcohol, n-butanol, iso-butanol, sec-butanol, tert-butanol, etc., are preferably used. The temp. fall of the rinse liquid and the generation of the scum, etc., occurring therein are prevented in this way and the possibility of the ignition, etc., in the developing and rinsing stage is eliminated. The rinse liquid for photosensitive polyimide which assures safe use is thus obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a rinsing solution used in a rinsing step for removing a developer in the development step of a photosensitive polyimide composition useful as an electronic material.

[Prior Art] Conventionally, lower alcohols such as methanol, ethanol, and isopropanol have been mainly used as rinsing liquids for photosensitive polyimide compositions.

However, when using spray development or puddle development, which are commonly used in semiconductor manufacturing processes, rinsing with a lower alcohol such as isopropanol will speed up the evaporation of the rinse solution. Sometimes, as the temperature of the rinsing liquid decreases, components dissolved by the developer adhere again, causing scum. Also,
In the case of such lower alcohols, the flash point is lower than the normal room temperature of a clean room, which is 25 degrees Celsius, so there is a drawback that there is a risk of ignition if a spark is generated from a developing device in this type of process. .

[Problems to be Solved by the Invention] The present invention has been devised in view of the various drawbacks of the prior art, and its purpose is to reduce the temperature of the rinsing liquid and the occurrence of scum etc. caused by this. It is an object of the present invention to provide a rinsing liquid for photosensitive polyimide that can be used safely without the risk of ignition during the development rinsing process.

[Means for Solving the Problems] An object of the present invention is to provide a method for developing a photosensitive polyimide in which a rinsing liquid used in a rinsing process for removing a developer is composed of a primary alcohol having 4 to 6 carbon atoms. This can be achieved using a photosensitive polyimide rinsing liquid with special characteristics.

In the present invention, primary alcohols having 4 to 6 carbon atoms include n-butanol, 1so-butanol, 5ec-butanol, tert-butanol, n-amyl alcohol,
1so-amyl alcohol, n-hexanol, is○
-Hexanol, cyclohexanol, etc. are preferably used. Among these, tert-butanol is used at 25°C.
Since it is a solid, it is preferable to mix it with other alcohol components when using it. Also,
Other than these may be used alone or in combination of two or more.

In addition, other organic solvents such as benzene, toluene,
Xylene, dioxane, tetrahydrofuran, methanol, ethanol, isopropanol, ethyl acetate, propyl acetate, butyl acetate, etc. can also be blended.

The rinsing liquid for photosensitive polyimide of the present invention can be applied to all currently known photosensitive polyimides (for example,
No. 52822, U.S. Patent No. 3957512, JP-A-2-50161, Proceedings of the Society of Polymer Science, p.8
07 (1990) etc.).

Next, a method for developing photosensitive polyimide using the rinsing liquid of the present invention will be explained.

First, a photosensitive polyimide film is applied onto a silicon wafer using a method such as a spin cord, and a solvent is scattered on a hot plate or in an oven. after that,
After a predetermined amount of exposure has been performed, the wafer is fixed on a spinner, and a developer is sprayed onto the spinner at 100 to 3,000,000 revolutions per minute (spray development). Alternatively, a developing solution is placed on the wafer on a spinner, and the wafer is left standing for development (paddle development). Other development methods include immersion development in which the wafer is immersed in a tank of developer solution, and irradiation with ultrasonic waves during immersion development.
Obtain a relief pattern.

After that, rinsing is performed using the rinsing liquid of the present invention. Rinsing methods include spraying a rinsing liquid onto a rotating wafer using a nozzle or sprayer (spray rinsing);
Although there are methods such as immersing the wafer in a bath of rinsing liquid or irradiating the wafer with ultrasonic waves during immersion, it is preferable to perform rinsing by a spray rinsing method due to the characteristics of the rinsing liquid of the present invention. After this rinsing step, a final product is obtained by heat treatment at about 100° C. to 450° C. in an oven or hot plate to convert it into polyimide.

[Examples] The present invention will be specifically described below based on Examples, but the present invention is not limited thereto.

Example 1 UR-3 manufactured by Toshiku Co., Ltd. as a photosensitive polyimide festival
140 on a 4-inch silicon wafer.
A spin code was run for 500,500 rotations. After that 80
After drying at ℃ for 1 hour, a 365nm test pattern 9-19A-1 manufactured by Dainippon Printing Co., Ltd. was used as a mask using contact aligner PLA-501 manufactured by Canon Co., Ltd.
Exposure was performed at a wavelength of 200 mJ/cm2.

This sample was subjected to paddle development using a clean track manufactured by Tokyo Electron Ltd. using a developer containing 70% by weight of N-methylpyrrolidone and 30% by weight of xylene.

The developing conditions were as follows: a developer was applied to the silicon wafer for 3 seconds at 100 revolutions, then left to stand for 5 minutes for development, and 1so-butanol was sprayed at 500 revolutions for rinsing.

During rinsing, the temperature at the center of the wafer was 20°C and the temperature at the periphery was 18°C in a 23°C clean room.

When the development results were observed with an optical microscope, no scum was observed from the center to the periphery, and the resolution was similar.

Example 2 A polyimide film was formed, developed, and rinsed in the same manner as in Example 1, except that n-butanol was used as the rinsing liquid.

During rinsing, the temperature at the center of the wafer was 20°C and the temperature at the periphery was 1°C in a 23°C clean room.

When the results of the development were observed with an optical microscope, no scum was observed from the center to the periphery, and a similar resolution was achieved.

Example 3 A polyimide film was formed, developed, and rinsed in the same manner as in Example 1, except that 1so-amyl alcohol was used as the rinsing liquid.

During rinsing, the temperature at the center of the wafer was 21°C and the temperature at the periphery was 19°C in a 23°C clean room.

When the results of the development were observed with an optical microscope, no scum was observed from the center to the periphery, and a similar resolution was achieved.

Example 4 is with tert-butanol as a rinse solution.

- Formation of a polyimide film in the same manner as in Example 1 except that a mixture of butanol at a volume ratio of 1:1 was used;
Developed and rinsed.

During rinsing, the temperature at the center of the wafer was 21°C and the temperature at the periphery was 19°C in a 23°C clean room.

When the results of the development were observed with an optical microscope, no scum was observed from the center to the periphery, and a similar resolution was achieved.

Example 5 A polyimide film was formed, developed, and rinsed in the same manner as in Example 1, except that a mixture of cyclohexanol and n-butanol in a volume ratio of 1:1 was used as the rinsing liquid.

During rinsing, the temperature at the center of the wafer was 21°C and the temperature at the periphery was 19°C in a 23°C clean room.

When the results of the development were observed with an optical microscope, no scum was observed from the center to the periphery, and a similar resolution was achieved.

Comparative Example 1 The same procedure as in Example 1 was carried out except that isopropanol was used as the rinsing liquid.

During rinsing, the temperature at the center of the wafer was 17°C and the temperature at the periphery was 1°C in a 23°C clean room.

When the image was observed using an optical microscope, scum was observed in several places from the center to the periphery of the large area of the blank.

[Effect of the invention] The present invention provides a rinsing liquid for photosensitive polyimide containing 1 to 1 carbon atoms.
By using No. 6 primary alcohol, it is possible to reliably prevent a drop in the temperature of the rinsing liquid and the generation of scum caused by this, and it can be used safely without fear of ignition during the development and rinsing process. There are advantages.

Claims (1)

[Claims] 1. A rinsing solution for photosensitive polyimide, characterized in that the rinsing solution used in the rinsing step for removing the developer in the photosensitive polyimide development step is composed of a primary alcohol having 4 to 6 carbon atoms.