Method of forming a pattern

Radiation imagery chemistry: process – composition – or product th – Imaging affecting physical property of radiation sensitive... – Forming nonplanar surface

Reexamination Certificate

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C430S331000

Reexamination Certificate

active

06818387

ABSTRACT:

CROSS-REFERENCE TO RELATED APPLICATIONS
This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2001-040618, filed Feb. 16, 2001, the entire contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method of forming a pattern, which is designed to be employed in the manufacture of a semiconductor device, a ULSI, an electronic circuit component, a liquid crystal display element, etc.
2. Description of the Related Art
Concomitant with an increasing fineness in dimension of semiconductor element and also with an increasing size in diameter of semiconductor substrate, the problems resulting from the conventional developing method, such as the generation of critical defects in a developed pattern, and the non-uniformity in dimension of pattern within the surface of a single semiconductor substrate of a single chip have become increasingly serious. In order to overcome these problems, various measures have been conventionally taken, such as the controlling of developing time, the improvement of developing solution, the employment of chemicals as a rinsing liquid, the extension of rinsing time, an increased repetition of rinsing, etc., which however inevitably invite the complication of pattern-forming process. Therefore, it is now desired to find out a novel method which is simpler in process and more effective.
According to the prior art, the developing step of semiconductor substrate after the processes of exposure and heat treatment has been generally performed by a method wherein a developing solution is directly ejected to the surface of semiconductor substrate to be treated to thereby initiate the development thereof. There is also known a developing process including a pretreatment wherein pure water is ejected to the surface of semiconductor substrate, after which the pure water remaining on the surface of the semiconductor substrate is shaken off by rotating the semiconductor substrate at a low speed so as to form a thin water layer on the surface of the semiconductor substrate, thus preliminarily wetting the semiconductor substrate and apparently improving the wettability of the surface of the semiconductor substrate to a developing solution. After this pretreatment, a developing solution is ejected to the surface of the semiconductor substrate to thereby perform the development.
Since a semiconductor substrate is enabled to wet by means of the pretreatment using pure water (hereinafter referred to as the pure water pretreatment), the developing solution can be prevented more or less from being repelled out of the surface of the semiconductor substrate, thereby making it possible to improve the in-plane uniformity of the layer of the developing solution. However, due to the demand for further enhancing the fineness of critical dimension, the problem of difference in dimension within a minute region that cannot be overcome by the conventional method is now raised, thereby necessitating the development of more precise developing process. Furthermore, concomitant with the enhancing fineness of critical dimension, the defects of pattern due to the conventional developing process are caused to frequently generate, thus raising a serious problem that the yield of semiconductor device is deteriorated. It is impossible, with the employment of the conventional developing process, to overcome these problems. It is also ineffective, even with the aforementioned pure water pretreatment, to overcome these problems.
As described above, concomitant with an increasing fineness in dimension of semiconductor element and also with an increasing size in diameter of semiconductor substrate, the non-uniformity in dimension of pattern within a minute region of the semiconductor substrate as well as all over the surface of the semiconductor substrate is caused to generate, thereby necessitating the development of more precise developing process. Additionally, it is also required to minimize the generation of critical defects in a developed pattern, that may be resulted from a developing process.
BRIEF SUMMARY OF THE INVENTION
(1) According to an aspect of the present invention, there is provided a method of forming a pattern:
coating a photosensitive resist film on a surface of substrate;
subjecting the photosensitive resist film to an exposure process;
coating an oxidizing liquid having an oxidative effect on a surface of the photosensitive resist film that has been subjected to the exposure process to thereby perform a pretreatment wherein the surface of the resist film is caused to oxidize by the oxidizing liquid to form an oxide layer thereon;
feeding a developing solution to the photosensitive resist film whose surface has been oxidized to thereby perform a development of the resist film; and
feeding a rinsing solution to a surface of the substrate to wash the substrate.
(2) According to an aspect of the present invention, there is provided a method of disposing a chemical liquid which has been employed in a treatment of a substrate:
feeding an alkaline solution to a chemical liquid-retaining portion which is disposed outside a substrate having a thin film formed on a main surface thereof;
feeding an aqueous solution of ozone to a main surface of the substrate to thereby reform a surface of the thin film, the aqueous solution of ozone which has been employed in the reforming being subsequently introduced into the chemical liquid-retaining portion where the alkaline solution is retained;
decomposing ozone of the aqueous solution of ozone that has been introduced into the chemical liquid-retaining portion by making use of the alkaline solution retained in the chemical liquid-retaining portion; and
discharging the alkaline solution and the aqueous solution of ozone where ozone has been decomposed from the chemical liquid-retaining portion.
(3) According to an aspect of the present invention, there is provided a method of forming a pattern:
feeding an alkaline solution to a chemical liquid-retaining portion which is disposed outside a substrate having a thin film formed on a main surface thereof;
feeding an aqueous solution of ozone to a main surface of the substrate to thereby reform a surface of the thin film, the aqueous solution of ozone which has been employed in the reforming being subsequently introduced into the chemical liquid-retaining portion where the alkaline solution is retained;
decomposing ozone of the aqueous solution of ozone that has been introduced into the chemical liquid-retaining portion by making use of the alkaline solution retained in the chemical liquid-retaining portion;
feeding an alkaline solution to the main surface of the substrate which has been surface-modified to thereby selectively etch the thin film by making use of the alkaline solution, the alkaline solution employed in the etching being subsequently retained in the chemical liquid-retaining portion; and
discharging the alkaline solution and the aqueous solution of ozone where ozone has been decomposed from the chemical liquid-retaining portion.
(4) According to an aspect of the present invention, there is provided a method of forming a pattern:
feeding an alkaline solution to a main surface of a substrate having a thin film formed on a main surface thereof to thereby selectively etch the thin film by making use of the alkaline solution;
retaining the alkaline solution which has been employed for the etching in a chemical liquid-retaining portion disposed outside the substrate;
feeding an aqueous solution of ozone to a main surface of the substrate which has been etched to thereby wash the main surface of the substrate, the aqueous solution of ozone which has been employed in the washing being subsequently introduced into the chemical liquid-retaining portion;
decomposing ozone of the aqueous solution of ozone that has been introduced into the chemical liquid-retaining portion by making use of the alkaline solution retained in the chemical liquid-retaining portion;
dryin

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