JPS6138945A - Peeling agent composition - Google Patents

Abstract

PURPOSE:To enable easy peeling of a positive type photoresist formed on an inorg. substrate in a short time without corroding the metals of the substrate and the like by using a compsn. composed of specified amts. of methylene chloride, metasulfonic acid, and aromatic sulfonic acid. CONSTITUTION:A compsn. used for peeling a positive type photoresist formed on the inorg. substrate is composed of 50-99wt% methylene chloride, 1-50wt% metasulfonic acid, and 1-50wt% aromatic sulfonic acid, such as monoalkylbenzenesulfonic acid or dialkylbenzenesulfonic acid, preferably, xylenesulfonic acid and dodecylbenzenesulfonic acid. The inorg. substrate can be easily peeled of the photoresist film in a short time by bringing said peeling agent compsn. into contact with the resist film formed on the substrate at 10-40 deg.C, and then, washing it with methanol or the like and further washing it with water.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stripping agent composition for stripping a positive photoresist film formed on an inorganic substrate.

Semiconductors and integrated circuits are manufactured by coating a photoresist on an inorganic substrate, exposing it to light, developing it to form a photoresist film, and then performing the necessary microfabrication such as etching and selective diffusion. It is manufactured by peeling and removing a photoresist film from a substrate.

In general, the above-mentioned photoresists include positive types that become solubilized by exposure to light and negative types that become insolubilized by exposure. Photoresists are known, and among negative-type photoresists, photoresists containing polyvinyl cinnamate or cyclized rubber as a resin component are known. In this way, as a stripping agent composition for forming a photoresist film on an inorganic substrate and peeling off the photoresist film after microfabrication, depending on the positive type or negative type, for example, Japanese Patent Application Publication No. Publication No. 57-51785 describes a compound consisting of methylene chloride and methanesulfonic acid,
A composition that has peeling strength at room temperature has been proposed, but with this stripper composition, the peeling speed of the photoresist film is slow, and the photoresist film becomes inorganic due to complete dissolution by the stripper composition. Rather than being exfoliated from the substrate, at least a portion remains undissolved in the composition and is thus exfoliated as flakes, which are then redeposited onto the inorganic substrate, resulting in this Semiconductor devices manufactured from such substrates may malfunction.

In particular, in recent years, in order to improve the processing accuracy of the substrate after photoresist film formation, the baking temperature of the photoresist film after development has tended to be increased. Methods such as plasma etching, reactive ion etching (RIE processing), and ion implantation tend to bond photoresist films more firmly onto inorganic substrates, including the stripping agent compositions described above. According to conventional stripping agent compositions,
A photoresist film treated in this manner cannot be easily and quickly peeled off at room temperature.

Therefore, in recent years, not only has the peeling speed become faster, but also the progress in the resist film formation process described above has made it possible to peel off and remove resist films firmly bonded to inorganic substrates at room temperature. or metals, e.g.
There is a growing demand for stripping agent compositions that are substantially non-corrosive to aluminum, nickel, and the like.

The present invention has been made in response to such demands, and includes not only conventional photoresist films but also positive photoresist films that are firmly bonded onto an inorganic substrate by plasma etching or ion implantation as described above. It is an object of the present invention to provide a novel stripping agent composition that can easily strip resist films in a short time and at room temperature.

The present invention provides a stripping agent composition for stripping a positive photoresist film formed on an inorganic substrate, comprising: (a) 60 to 99% by weight of methylene chloride; (b)
(c) 1 to 50% by weight of methanesulfonic acid; and (c) 1 to 50% by weight of at least one aromatic sulfonic acid selected from the group consisting of benzenesulfonic acid, monoalkylbenzenesulfonic acid, and dialkylbenzenesulfonic acid. shall be.

In the present invention, inorganic substrates include silicon dioxide, silicon, sapphire, silicon with a silicon coating, silicon nitride, gallium-arsenide (gallium arsenide), gallium-gadolium-garnet (cGG), and silicon dioxide with a chromium oxide coating. , nickel, chromium, and aluminum with conductive metal coatings.

In addition, in the present invention, the polymer forming the positive photoresist film is not particularly limited, but the stripping agent composition according to the present invention is particularly suitable for forming a positive photoresist film containing a novolac type cresol resin as a polymer component. It can be suitably used for peeling.

The stripper composition according to the invention contains from 50 to 99% by weight, preferably from 60 to 80% by weight, of methylene chloride, based on the composition. When the content of methylene chloride is out of the above range, a sufficiently strong peeling force will not be obtained in any case. It also contains methanesulfonic acid in an amount of 1 to 50% by weight, preferably 10 to 30% by weight.

Next, the stripping agent composition according to the present invention contains 1 to 50% by weight, preferably 10 to 30% by weight, of aromatic sulfonic acid. This aromatic sulfonic acid is at least one type selected from the group consisting of benzenesulfonic acid, monoalkylbenzenesulfonic acid, and dialkylbenzenesulfonic acid, and as monoalkylbenzenesulfonic acid, it has 1 carbon number.
An alkylbenzenesulfonic acid having 1 to 14 linear or branched alkyl groups is preferred, and for example, toluenesulfonic acid, propylbenzenesulfonic acid, dodecylbenzenesulfonic acid, etc. are preferably used. Further, as the dialkylbenzenesulfonic acid, a dialkylbenzenesulfonic acid having a linear or branched alkyl group having 1 to 14 carbon atoms and a lower alkyl group having 1 to 4 carbon atoms is preferable, and xylene sulfonic acid is particularly preferable. Preferably used.

Such aromatic sulfonic acids not only increase the stripping power of the stripping agent composition, but also substantially eliminate the corrosivity of the stripping agent composition consisting of methylene chloride and methanesulfonic acid to metals, and thus have practical value. It provides a high release agent composition.

The stripping agent composition according to the present invention is usually applied to a positive photoresist film on an inorganic substrate at a temperature of 10 to 40°C, washed with a lower alcohol such as methanol or isopropanol, and washed with water. After rinsing and drying, it is possible to obtain a substrate from which the positive photoresist film has been completely peeled off.

As described above, the stripping agent composition of the present invention can easily and quickly strip a resist film on an inorganic substrate at room temperature, and is substantially corrosive to both the substrate and metal. It has no gender.

The release agent composition according to the present invention will be explained below with reference to Examples.

Example 1 A positive photoresist consisting of a novolac type phenol resin and a photosensitizer was applied using a spinner onto a silicon wafer on which a silicon dioxide film was formed on the surface by steam oxidation, and heated at a temperature of 95°C for 30 minutes. After pre-baking, post-baking was carried out by heating at a temperature of 160° C. for 30 minutes to form a photoresist film with a thickness of 1.2 μm.

Next, these photoresist films were immersed in a stripping agent composition having the composition shown in Table 1 at a predetermined temperature for a predetermined time, washed with methanol, rinsed with water, and dried by infrared irradiation. The peeling speed and peeling time of the photoresist were determined by irradiating the substrate with monochromatic light or observing it with an optical microscope at a magnification of 400 to 800 times to determine whether there was any remaining photoresist on the substrate. The results are shown in Tables 2 to 5.

Example 2 In the same manner as in Example 1, a positive photoresist was applied onto a silicon wafer, prebaked at a temperature of 90°C for 30 minutes, and post-haked at 140°C for 30 minutes to a thickness of 1.
A photoresist film of μm thickness was formed. This film is approximately Q,
Plasma etching treatment was performed under a tetrafluoromethane gas atmosphere of 1 Torr (13.56MH2, 200
W).

This photoresist film was immersed in a stripping agent composition in the same manner as in Example 1, and the peeling speed and peeling time of the photoresist film were determined. The results are shown in Table 6.

Procedural amendment (spontaneous) June 25, 1985 Application No. 09831) 2, Name of the invention: Stripping agent composition 3, Relationship with the case of the person making the amendment Address of patent opponent Nishi-ku, Osaka City 1-1-17 Shinmachi Name: Nagase Sangyo Co., Ltd. 4 Agent address: 1-8-3-5 Shinmachi, Nishi-ku, Osaka Date of amendment order: Showa, month, day (Shipping date: Showa
Contents of the amendment (1) The phrase "In particular, for the purpose of..." from page 3, line 18 of the specification to page 5, line 2 of the specification is amended as follows.

"In particular, in recent years, in order to improve the processing accuracy of the substrate after photoresist film formation, the post-bake temperature of the photoresist film after development has been increased, or the photoresist film has been irradiated with deep ultraviolet rays after pre-bake or post-bake. The resist film tends to be more highly hardened.Furthermore, LSI
, VLSI, etc., as the degree of integration of devices increases, the substrate after photoresist film formation is subjected to plasma etching, reactive ion etching (RIE processing),
Using processing techniques such as ion implantation, finer and more sophisticated processing is becoming commonplace, but in such processing, the photoresist film near the substrate being processed is subject to high-temperature thermal history and deteriorates. , including the stripping agent compositions described above;
According to conventional stripping agent compositions, photoresist films that have been subjected to heat history in this manner are not easily and quickly stripped.

Therefore, in recent years, not only is the peeling speed faster, but also the highly hardened photoresist film as described above and the photoresist film that has undergone thermal history due to microfabrication of the substrate can be peeled off at room temperature. There is a growing demand for stripping agent compositions that are substantially non-corrosive to inorganic substrates and metals, such as aluminum and nickel.

The present invention was made in response to such demands, and includes not only conventional photoresist films but also photoresist films that are highly hardened or subjected to thermal history due to microfabrication of the substrate as described above. Another object of the present invention is to provide a novel stripping agent composition that can be easily and quickly stripped at room temperature. (2) In Table 2 on page 10 of the specification, rKPRJ in the photoresist column and (note) column is replaced by rKMPRJ.
and correct it.

(3) In Table 3 on page 1 of the specification, rK'PRJ in the photoresist column and the (note) column is corrected to rKMPRJ.

(4) In Table 4 on page 12 of the specification, rKPRJ in the photoresist column is corrected to ro F P RJ.

(5) In Table 4 on page 12 of the specification, rKPR800 in the (note) column is a positive photoresist manufactured by Eastman Kogutsu. " rOFPR800 is manufactured by Tokyo Ohka Kogyo ■. ” he corrected.

(6) In Table 6 on page 14 of the specification, rKPRJ in the photoresist column is corrected to rKMPRJ.

Written amendment to the above procedure (method) % formula % 2. Name of the invention Stripping agent composition 3. Relationship with the person making the amendment Patent applicant address 1-1-17 Shinmachi, Nishi-ku, Osaka Name Nagase Sangyo Co., Ltd. 4. Agent address: 1-8-3-6 Shinmachi, Nishi-ku, Osaka City; Number of inventions to be increased by the amendment; 7; Subject of the amendment: June 25, 1985: Amendment to submission procedure (voluntary) June 1985 25th

Claims (3)

[Claims] (1) In a stripping agent composition for stripping a positive photoresist film formed on an inorganic substrate, (a) 50 to 99% by weight of methylene chloride, (b) 1 to 50% by weight of methanesulfonic acid, and (c) 1 to 50% by weight of at least one aromatic sulfonic acid selected from the group consisting of benzenesulfonic acid, monoalkylbenzenesulfonic acid, and dialkylbenzenesulfonic acid. (2) At least one aromatic compound selected from the group consisting of (a) 60 to 80% by weight of methylene chloride, (b) 10 to 30% by weight of methanesulfonic acid, and (c) monoalkylbenzenesulfonic acid and dialkylbenzenesulfonic acid. 10-30% by weight of sulfonic acid, The stripping agent composition according to claim 1, comprising: 10 to 30% by weight of sulfonic acid. (3) Claim 1 or 2, characterized in that the aromatic sulfonic acid is at least one selected from xylene sulfonic acid and dodecylbenzenesulfonic acid.
The stripping agent composition described in Section 1.