JPS62231250A - Resist material - Google Patents

Abstract

PURPOSE:To obtain a positive type resist material high in sensitivity and oxygen plasma resistance by reacting sulfonyl chloride with the unreacted hydroxyl group remaining in siloxane polymer obtained by hydrolyzing and dehydration condensing a specified silane compound. CONSTITUTION:The resist material is obtained by reacting naphthoqhinone-1,2- diazido-5-sulfonyl chloride or naphthoquinone-1,2-diazido-4-sulfonyl chloride with the unreacted hydroxyl group remaining in the siloxane polymer obtained by hydrolyzing and dehydration condensing the silane compound represented by the formula shown on the right in which R is optionally substituted alkyl or such aryl, and X is Cl, methoxy, or ethoxy. The use of resist material having the polysiloxane structure as the main chain structure permits oxygen plasma resistance to be extremely enhanced and a fine positive pattern high in aspect ratio to be obtained.

Description

Detailed Description of the Invention ° [Industrial Field of Application] The present invention relates to resist materials C2 that can be used to manufacture semiconductor devices, magnetic/(lube devices, optical application parts, etc.) In order to form high-definition, high-aspect-ratio patterns, the resist is
A method of creating a layered structure has been proposed.

That is, a thin upper resist layer is placed on the lower resist layer of the organic polymer layer material, and after forming a turn on the upper resist layer material, the organic polymer layer is further etched using gas plasma C: using it as a mask. This upper layer resist I
: Oxygen plasma resistance I: Excellent (- requires high sensitivity and high resolution) Oxygen plasma resistance 1: Excellent silicon-containing polymer 6: Highly sensitive group introduced 9 resist materials are promising being watched.

The material used is a silica-sun polymer with a cylindrical structure (2,6-bis (as a two-layer sensitizer)).
It has been reported that a photosensitive resin composition containing p-azidobenzal)-4-methylcyclohexanone is superior [Tanaka et al.
985) Ko.

However, this material has the drawbacks of being a negative resist, such as rounding, poor resolution (difficult to form fine patterns), and difficulty in peeling off the resist pattern after processing the substrate.

For this reason, positive resists containing Sl that are non-swellable and capable of alkaline development are viewed as promising.

As this positive resist, a novolak resin-polymer into which a disilyl group has been introduced has been reported.

(Ito et al., Proceedings of the 32nd Applied Physics Conference 29p-H-15 (1985)) However, the positive resist with 81 has a low content (and Sl is introduced in the side chain 1). Therefore, the resistance to +IHC plasma is not sufficient, so the upper layer positive resist needs to be thicker in order to use it as a mask when etching the lower layer resist, so it is not expected to improve resolution much. There is a drawback.

[Purpose of the invention]

The present invention has been developed in view of the circumstances (g) and it is an object of the present invention to provide a positive resist material which is highly sensitive and highly resistant to oxygen plasma.

[Means for solving the problems] Therefore, the present invention (with the following general formula CI) X-8i
-X -------(1) (In the formula, Rf1 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic group. Also, X is ct, 0CH3QC
Ifl selected from the 2H5(7) group are shown. ) is hydrolyzed and further subjected to dehydration condensation.C: In the siloxane polymer obtained from Using a reaction product obtained by reacting naphthoquinone and 1,2-diazide-4-sulfonyl chloride as a resist material C:
We have tried to solve the above problems.

Typical examples of the trifunctional silane represented by the general formula CI) include 7-eltrical silane, phenyltrimethoxysilane, and phenyltriethoxysilane. 1 and 42, a polysilsesquioxane represented by the following general formula (1) is obtained.

-------(1) (However, in the formula, Rtt represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic group, and n is an integer of 1 or more.) As shown in the above-mentioned Sakakizo formula, the water group that cannot contribute to the condensation reaction and remains unreacted in the molecule is located at the end of the molecule or at other sites.
:exist. ? :, glue type polysiloxane/rl,
51 Because C silicon dioxide 7 sites are easily formed on the surface by elemental plasma etching, the etching resistance is high. A part or all of the unreacted water groups remaining at the site are reacted with naphthoquinone-1゜2-diazide-5-sulfonyl chloride or naphthoquinone-1,2-diazide-4-sulfonyl chloride, and the hydroxyl groups are converted into the corresponding naphthoquinone-5-sulfonyl chloride. Quinonediazide sulfonic acid ester and nine.

The polysilsesquioxane of general formula (1) into which naphthoquinonediazide sulfonic acid ester is introduced is insoluble in aqueous alkali solution I. However, these naphthoquinone compounds are rounded and converted into the corresponding indenecarboxylic acid by irradiation with Takaniki Lugie radiation such as ultraviolet rays, and the polysilsesoxane after irradiation becomes soluble in an aqueous alkali solution of 1:1.

For this reason, polyphenylsilsesquioxane introduced with naphthoquinonediazide sulfonic acid ester is irradiated with energy rays (a pair of positive-type custom-made products is shown).

As described above, since the main chain of the resist material of the present invention has a polysiloxane structure, the resistance to oxygen plasma is extremely high.
l; (Positive type allows formation of a pattern with a slightly finer pattern and a high aspect ratio.

[Production Example] Hereinafter, a production example of the resist material of the present invention will be shown, but the present invention is not limited thereto.

(Production Example 1) Dissolve 0.04 mol of phenyltrichlorosilane in 40 ml of N-methylpyrrolidone, and add 10 ml of water while stirring.
-Add. After leaving for 1 hour, add 1:50 ml of water. At this time, polymer precipitation occurs.

The supernatant was removed by decantation 1, and the precipitated polymer was washed with water. 5. Dissolve the polymer in 10% of tetrahydrofuran. C in methanol-water; the solution was added dropwise to obtain a white polymer. The infrared absorption spectrum of this polymer (: siloxane bond C: has a characteristic large absorption at 1000 to 1200 cm-16;
4.4 g of the 1st polymer and naphthoquinone-1,2-diazide °-5-sulfonyl chloride 10. It was confirmed that there was an absorption based on the stretching movement of the hydroxyl group in the vicinity of Ocm-' and that the structure was of the general formula (1). Dissolve 8 g of dioxane in 90 m of dioxane (while stirring).
At a temperature of 10°C, gradually add 40ml of a 10% aqueous solution of sodium carbonate. A white precipitate will form immediately, so if you stir it for about 2 hours, the precipitate will turn into a sticky oily substance 1-f.
Waru. Remove the supernatant using the decanting method, add about 10 times the amount of water, and add it to the water. A resist material of the present invention was obtained.

(Production I12) Production Example II Naphthoquinone-1,2-diazide
Instead of 5-sulfonyl chloride (-naphthoquinone-1
A similar method was used to obtain a resist material in which 7-toquinone dioxycytosulfonic acid ester was introduced.

[Experiment example]

Next, the effects of the resist material of the present invention will be explained more clearly in a different experimental example C.

(Experimental Example 1) An ethyl cellosolve solution of the resist material obtained in Production Examples 1 and 2 was coated on a 81 wafer C to a thickness of about 0.2 μm using spin code method 6, and prebaked at 80° C. for 20 minutes. . After prebaking, ultraviolet rays were irradiated using an Oak jet light.

After irradiation, each sample was developed with a developer containing Microposit 2401 (manufactured by Sibley) and water at a ratio of 1/1, and the irradiation amount at which the residual film on the irradiated area was 0 was defined as the sensitivity.

The irradiation amount is shown in Table 1g. The resolution was evaluated by forming a cross-in and space pattern, and a pattern with a width of 0.5 μm could be formed with each material.

(Experimental Example 2) Example IC 2: 9g of ultraviolet irradiation; Electron beam irradiation was performed and irradiation 1, where the residual film in the irradiated area becomes O, was determined using the method similar to rt1. The results are shown in Table 2. .

(Experimental Example 3) CXS irradiation was performed instead of ultraviolet IR irradiation in Example fIlII;, and the irradiation amount at which the remaining film in the irradiated area was () was determined in the same manner. The results are shown in Table 3.

〔Effect of the invention〕

As explained above, since the V cyst material of the present invention has a polysiloxane structure, it has a very high diatomic plasma resistance of 1:1, and is advantageous for forming fine patterns. Sarashi:
, is a naphthoquinonediazide sulfonate ester, which is converted to indene carbonate by energy ray irradiation, so it has the advantage of becoming a highly sensitive positive resist that can be developed in Al direction.

Since it is a positive type, it has the advantage that the resist pattern can be easily peeled off after processing the substrate.

Applicant Believe in Japan 1! Story Co., Ltd. 1 *02 pressure 10 m 'l'o! ”r O,I W/cm
”Table 2 Table 3

Claims (1)

[Claims] The following general formula, ▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, R represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group.
One type selected from the group CH_3OC_2H_5 is shown. ) Naphthoquinone-1,2-diazide-5-
Sulfonyl chloride or naphthoquinone-1,2-
A resist material made by reacting diazide-4-sulfonyl chloride.