JPS60117242A - Micropattern forming material - Google Patents

Abstract

PURPOSE:To enhance resolution and to form a micropattern by using, as an ionizing radiation-sensitive resist and a photosensitive resist, a compsn. obtained by esterifying a specified ladder type polyorganosiloxane with axidobenzoyl chloride or its deriv. CONSTITUTION:A compsn. to be used as an ionizing radiation-sensitive resist and a photoresist is obtained by esterifying azidobenzoyl chloride or its deriv. with a ladder type polyorganosiloxane represented by the formula in which R1 is phenyl, methyl, or phenyl/methyl, and R2 is hydroxyalkyl or -(-CH2)nOH, and (n) is 1-5. A proper content of azide groups in the ladder type polysiloxane is 0.5- 15mol% of the total monomers used for composing the polymer, and when <0.5 mol%, a cross-linking effect is lessened, and when >15mol%, mechanical strength of the cross-linked resist film lessened. A preferable wt. average mol.wt. of the polymer is in the range of 2,500-7,000, and in this range a good resist film can be obtained by the spin coating method.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Technical Field of the Invention The present invention relates to compositions of ionizing radiation resists and photosensitive 111' resists suitable for forming fine patterns.

(b) Background of the technology The degree of integration of semiconductor devices such as ICs and LSIs is increasing, and as a result, unit elements are becoming smaller and wiring pattern widths are also decreasing.
The pattern is about to be put into practical use.

The present invention relates to a resist composition that has good resolution and is suitable for forming fine patterns.

(c) Prior art and problems Polyorganosiloxane is known as silicone resin and consists of inorganic negative 83-0-8t bonds and monovalent groups, so the physical and chemical properties of this material are inorganic. It has both organic and organic properties.

That is, heat resistance is due to silicon dioxide (SiOz), and solubility and plasticity are due to the presence of organic groups, and it is known as an excellent coating composition.

The present invention relates to a resist for forming fine patterns which is mainly made of this silicone resin.

Until now, resists using silicone resin as the main material for forming JTL have been developed.

For example, Japanese Patent Publication No. 55-37744 discloses a chain azide polyorganosiloxane as a composition for dry lithography.

However, as described in the text as a high viscosity polymer, this material has a high viscosity and is not suitable as a resist for forming fine patterns, which is the object of the present invention.

Furthermore, Japanese Patent Publication No. 57-12057 discloses a silicone compound in which an unsaturated vinyl ester is bonded to a terminal hydroxy ladder type organosiloxane. Because polymerization occurs in a chain reaction when exposed to light, it is not considered suitable for use in forming fine patterns with good resolution.

(d) Purpose of the Invention The purpose of the present invention is to provide a resist for ionizing radiation and a photosensitive resist that has a polyorganosiloxane as its main phase and has good resolution and is suitable for forming fine patterns.

(o) Structure of the Invention The purpose of the present invention is to use a composition obtained by esterifying a polyladder type organosiloxane represented by the general formula (1) and azidobenzoic acid chloride or a derivative thereof to produce a resist for ionizing radiation and a photosensitive resist. This can be achieved by using it as

Here, R,... phenyl group, methyl group, or phenyl group/
Methyl group rt, =-hydroxyalkyl group -(-CII,)
nOH, where n=1 to 5 (f) Embodiments of the Invention The present invention uses polyorganosiloxane as the polymer base, but since linear polyorganosiloxane is a highly viscous polymer, it is thermally unstable. The pattern may flow, making it unsuitable for forming fine patterns.

Therefore, polyladder type organosiloxane, which can form a relatively hard film, is used as the main constituent material.

Next, to impart photosensitivity, it is best to add various photosensitizers to each azide compound for electron beams and X-rays.

It is known as a crosslinking agent for ultraviolet rays, and according to the inventors' examination, it is characterized by a high resolution of the resist compounded because there is little chain reaction during exposure.

However, it is difficult to uniformly blend an azide compound into a polyorganosiloxane, and there is a problem that the azide compound may precipitate.

Therefore, in the present invention, polyorganosiloxane is converted into an azide surface.

The method for producing the polyorganosiloxane and the azide compound, which are the main constituent phases related to the present invention, and the method for converting the polyorganosiloxane into an azide are already known.

For example, the production of a polyladder type organosiloxane in which R2 in the general formula (1) is a hydroxyalkyl group, which is described in the claims, is disclosed in Kakai 54)-50645, and the production method of azidobenzoic acid chloride is published in the UK. Time 1 work 1
, 089, 095, and the production of azidated polyorganosiloxanes is disclosed in Japanese Patent Publication No. 55-37744.

Therefore, by partially modifying and using these production methods, the azidated polyladder type A-kanosiloxane according to the present invention can be produced.

The method for manufacturing a resist according to the present invention will be explained below with reference to Examples.

Example: Hydroxyethyltriethoxysilane (95 mol C%) and hydroxyethyltriethoxysilane (5 mol C%) were thermally polymerized in diphenyl ether using caustic potash (KOH) as a catalyst to produce a ladder-type organosiloxane polymer.

The produced polymer was reprecipitated with methyl ethyl ketone and ethanol, thoroughly washed, and then dried in vacuum.

Next, this polymer and m-sulfonyl azide benzoic acid chloride were dissolved in methylene chloride, and anhydrous pyridine diluted with methylene chloride was added dropwise thereto for esterification.

The esterified product was reprecipitated and washed with a small amount of acetone and ethanol, further washed with a large amount of water, and then vacuum-dried.

Next, as a pattern formation method, the azide polyladder type organosiloxane prepared by the above manufacturing method is dissolved in xylene, and silicon (Si) is formed by a spin code method.
It was coated onto a wafer to a film thickness of 0.5 [μm].

Next, prepay for 20 minutes at 80 C0C'3,
When this was exposed to an electron beam at an accelerating voltage of 20 (KV) and developed with xylene, a sensitivity of 5 μc/cJ1 was obtained.

The sensitivity was about 5 times higher than that without azide.

Note that when not azidized, it is not photosensitive, but by azidizing it, it is exposed to ultraviolet light having a wavelength of 365 (nm) at a sensitivity of 30 (mJ/c).

Note that azidated polyladder type siloxane can be prepared by the same method as above using methyltriethoxysilane or a mixture of methyltriethoxysilane and phenyltriethoxysilane as a raw material, but the sensitivity is higher with more methyl groups. In good condition.

Next, the content of azide groups in the azidated polyladder type siloxane prepared in this way is suitably 05 to 15 moles [1] based on the total monomers constituting the polymer.
．． If the amount is less than 5 moles, the crosslinking effect will be small, while if it is more than 15 moles, the mechanical strength of the crosslinked resist film will decrease.

The weight average molecular weight (Mw) of the shredded polymer is 2.
A value of 500 to 7,000 is good, and within this range, it is possible to obtain a 1:0 good coating film in the spin code method.

(9) Effects of the Invention The present invention provides a resist composition that has good resolution and is capable of forming fine patterns. can be obtained.

Claims (1)

[Claims] A composition obtained by esterifying a polyladder-type organosiloughisan represented by the general formula (■) and azidobenzoic acid chloride or a derivative thereof is used as γIj: a resist for radiation-absorbing radiation and a photosensitive resist. A fine pattern forming HJ material characterized by: General formula l Here, R1... Phenyl group, methyl group r xt tj: Phenyl group/methyl group R2... Hydroxyalkyl group +C)It)nO
H However, n=1~5