Radiation imagery chemistry: process – composition – or product th – Imaging affecting physical property of radiation sensitive... – Radiation sensitive composition or product or process of making
Reexamination Certificate
2001-06-07
2004-06-22
Ashton, Rosemary (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Imaging affecting physical property of radiation sensitive...
Radiation sensitive composition or product or process of making
C430S905000, C430S910000
Reexamination Certificate
active
06753124
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a radiation-sensitive resin composition and, more particularly, to a radiation-sensitive resin composition suitable as a chemically-amplified resist useful for microfabrication utilizing various types of radiation, for example, deep ultraviolet rays such as a KrF excimer laser or ArF excimer laser, X-rays such as synchrotron radiation, or charged particle rays such as electron beams.
2. Description of the Background Art
In the field of microfabrication represented by fabrication of integrated circuit devices, a lithographic technology enabling microfabrication with a line width of 0.20 &mgr;m or less has been demanded in order to achieve higher integration.
A conventional lithographic process utilizes near ultraviolet rays such as i-line as radiation. It is known in the art that microfabrication with a line width of sub-quarter micron is very difficult using near ultraviolet rays.
Therefore, use of radiation with a shorter wavelength has been studied for enabling microfabrication with a line width of 0.20 &mgr;m or less. As radiation with a shorter wavelength, deep ultraviolet rays represented by a line spectrum of a mercury lamp and an excimer laser, X-rays, electron beams, and the like can be given. Of these, a KrF excimer laser (wavelength: 248 nm) and an ArF excimer laser (wavelength: 193 nm) have attracted attention.
As a radiation-sensitive resin composition applicable to the excimer laser radiation, a number of compositions utilizing a chemical amplification effect between a component having an acid-dissociable functional group and a component generating an acid (hereinafter called “photoacid generator”) which generates an acid upon irradiation (hereinafter called “exposure”) has been proposed. Such a composition is hereinafter called a chemically-amplified radiation-sensitive composition.
As the chemically-amplified radiation-sensitive composition, Japanese Patent Publication No. 27660/1990 discloses a composition comprising a polymer containing a t-butyl ester group of carboxylic acid or a t-butylcarbonate group of phenol and a photoacid generator. This composition utilizes the effect of the polymer to release a t-butyl ester group or t-butyl carbonate group by the action of an acid generated upon exposure to form an acidic group such as a carboxylic group or a phenolic hydroxyl group, which renders an exposed area on a resist film readily soluble in an alkaline developer.
Most of conventional chemically-amplified radiation-sensitive compositions use a phenol resin as a base resin. Deep ultraviolet rays used as radiation for exposure are absorbed due to an aromatic ring in the resin and cannot sufficiently reach the lower layers of the resist film. Because of this, the dose of the radiation is greater in the upper layers and is smaller in the lower layers of the resist film. This causes a resist pattern to be thinner in the upper portion and be thicker toward the lower portion, thereby forming a trapezoid shape after development. No sufficient resolution can be obtained from such a resist film. Such a trapezoid shape formed after development cannot give a desired dimensional accuracy in the succeeding steps such as an etching step and an ion implantation step. In addition, if the configuration of the resist pattern is not rectangular on the upper portion, the resist disappears faster during dry etching, making it difficult to control etching conditions.
The shape of the resist pattern can be improved by increasing the radiation transmittance through the resist film. For example, (meth)acrylate resins represented by polymethylmethacrylate are desirable from the viewpoint of radiation transmittance due to the superior transparency to deep ultraviolet rays. Japanese Patent Application Laid-open No. 226461/1992 proposes a chemically-amplified radiation-sensitive resin composition using a methacrylate resin. However, in spite of the excellent micro-processing performance, this composition exhibits only poor dry etching resistance due to the absence of an aromatic ring, giving rise to difficulty in performing etching with high accuracy. This composition thus does not have both radiation transmittance and dry etching resistance at the same time.
A method of introducing an aliphatic ring into the resin component in the composition instead of an aromatic ring has been known as a means for improving dry etching resistance without impairing radiation transmittance of the resist made from a chemically-amplified radiation-sensitive resin composition. A chemically-amplified radiation-sensitive resin composition using a (meth)acrylate resin having an alicyclic ring is proposed in Japanese Patent Application Laid-open No. 234511/1995, for example.
This composition, however, comprises groups which are comparatively easily dissociated with conventional acids (for example, an acetal functional group such as a tetrahydropyranyl group) and groups which are comparatively difficult to be dissociated with acids (for example, a t-butyl functional group such as a t-butyl ester group, t-butylcarbonate group) as an acid-dissociable functional group as the resin component. The resin component possessing the former acid-dissociable functional group exhibits excellent basic characteristics as a resist such as superior sensitivity and excellent pattern shape, but has a problem of poor storage stability. In addition, the resin component possessing the former acid-dissociable functional group exhibits impaired resist characteristics, particularly in terms of sensitivity and pattern shape, in spite of excellent storage stability. In addition, inclusion of an alicyclic structure in the resin components of this composition increases hydrophobicity of the resin, resulting in poor adhesion to substrates.
More recently, several chemically amplified radiation sensitive compositions in which resin components having a lactone ring structure are used have been proposed. For example, Japanese Patent Applications Laid-open No. 239846/1998, No. 274852/1998, No. 12326/1999, and No. 223950/1999 disclose compositions containing a resin component in which the lactone ring structure is bonded at the 2-position (&agr;-position) and a photo acid generator. Japanese Patent Applications Laid-open No. 90637/1997 and No. 319595/1998 disclose compositions containing a resin component in which the lactone ring structure is bonded at the 3-position (&bgr;-position) and a photoacid generator. Japanese Patent Application Laid-open No. 207069/1998 discloses compositions containing a resin component in which the lactone ring structure is bonded at the 2 or 3-position and a photoacid generator.
However, most of these chemically amplified radiation sensitive compositions contain a resin component in which the lactone ring structure is bonded mainly at the 2-position, and some compositions at the 3-position. Although the resin components used in conventional chemically amplified radiation sensitive compositions contain a variety of functional groups mentioned above, these compositions have both merits and demerits in the performance as a resist. In addition, as indicated in Japanese Patent Application Laid-open No. 239846/1998, there are no established design standards for an acid-decomposable functional group protecting a carboxyl group, for example.
In view of recent progress in the microfabrication of semiconductor devices, development of a novel resin component exhibiting high transmittance of radiation, having excellent basic properties as a resist, and suitable for use in chemically amplified radiation sensitive compositions which can be adapted to short wavelength radiation represented by a deep ultraviolet rays is an important subject.
Therefore, an object of the present invention is to provide a radiation-sensitive resin composition usable as a chemically amplified positive tone resist, which has high transmittance of radiation, exhibits superior basic properties as a resist such as high sensitivity, resolution, and pattern shape, and is c
Douki Katsuji
Kajita Toru
Nishimura Yukio
Shimokawa Tsutomu
Ashton Rosemary
JSR Corporation
Kelber Steven B.
Piper Rudnick LLP
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