Radiation imagery chemistry: process – composition – or product th – Imaging affecting physical property of radiation sensitive... – Forming nonplanar surface
Reexamination Certificate
2002-01-02
2004-07-20
Hoff, Mark F. (Department: 1756)
Radiation imagery chemistry: process, composition, or product th
Imaging affecting physical property of radiation sensitive...
Forming nonplanar surface
C430S326000, C430S270100, C430S927000
Reexamination Certificate
active
06764811
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to a pattern formation method for forming a resist pattern made from an unexposed portion of a resist film of a chemically amplified resist material by irradiating the resist film with extreme UV of a wavelength of a 1 nm through 30 nm band through a mask.
In accordance with the increased degree of integration and downsizing of semiconductor integrated circuits, lithography technology is desired to be further developed in the process for semiconductor integrated circuit devices.
The exposing light for use in the lithography is now a mercury lamp, KrF excimer laser (of a wavelength of a 248 nm band) or ArF excimer laser (of a wavelength of a 193 nm band). However, for the generation of 0.1 &mgr;m or less, in particular the generation of 0.05 &mgr;m or less, use of extreme UV of a wavelength (of a 1 nm through 30 nm band) shorter than that of the ArF excimer laser is under examination.
In the lithography using the extreme UV as the exposing light, a chemically amplified resist material with high resolution and high sensitivity is preferably used.
Therefore, in the lithography using the extreme UV, a chemically amplified resist material suitably used in using the ArF excimer laser, whose wavelength is close to that of the extreme UV, is being examined to be used.
Now, a pattern formation method using a chemically amplified resist material suitable to the ArF excimer laser will be described with reference to
FIGS. 3A through 3D
.
First, a chemically amplified resist material having the following constituent is prepared:
Base polymer: poly((2-methyl-2-adamantyl methacrylate)-(methyl methacrylate)-(methacrylic acid)), wherein 2-methyl-2-admantyl methacrylate:methyl methacrylate:methacrylic acid=70 mol %:20 mol %:10 mol % . . . 2 g
Acid generator: triphenylsulfonium triflate . . . 0.4 g
Solvent: propylene glycol monomethyl ether acetate . . . 20 g
Next, as shown in
FIG. 3A
, the chemically amplified resist material having the aforementioned constituent is applied on a semiconductor substrate
1
, so as to form a resist film
2
with a thickness of 0.2 &mgr;m.
Then, as shown in
FIG. 3B
, the resist film
2
is irradiated with extreme UV
4
(of a wavelength of a 13 nm band) through a reflection mask (not shown) having a desired mask pattern for pattern exposure. After the pattern exposure, as shown in
FIG. 3C
, the resist film
2
is subjected to baking (PEB) with a hot plate at a temperature of 100° C. for 60 seconds.
In this manner, an exposed portion
2
a
of the resist film
2
becomes soluble in an alkaline developer owing to the function of an acid generated from the acid generator while an unexposed portion
2
b
of the resist film
2
remains refractory in the alkaline developer because no acid is generated from the acid generator.
Subsequently, the resist film
2
is developed with an alkaline developer, such as a 2.38 wt % tetramethylammonium hydroxide developer. Thus, a resist pattern
5
is formed from the unexposed portion
2
b
of the resist film
2
as shown in FIG.
3
D.
However, since the exposed portion
2
a
of the resist film
2
is irradiated with the extreme UV
4
with high energy during the pattern exposure, a crosslinking reaction is caused in the base polymer in the exposed portion
2
a
of the resist film
2
. Therefore, the exposed portion
2
a
of the resist film
2
cannot be completely dissolved in the alkaline developer, resulting in forming the resist pattern
5
in a defective shape as shown in FIG.
3
D.
When the resist pattern
5
is in a defective shape, the shape of an interconnect pattern formed by using the resist pattern
5
as a mask also becomes defective, which leads to a problem of poor yield of semiconductor devices.
SUMMARY OF THE INVENTION
In consideration of the aforementioned conventional problem, an object of the invention is forming a resist pattern made from an unexposed portion of a resist film in a good shape by suppressing a crosslinking reaction in an exposed portion of the resist film although pattern exposure is carried out through irradiation with extreme UV with high energy.
In order to overcome the problem, the first pattern formation method of this invention comprises the steps of forming a resist film of a chemically amplified resist material including a base polymer having a lactone group and having neither a hydroxyl group nor a carboxylic group as an adhesion group bonded to a polymer side chain, and an acid generator for generating an acid through irradiation with light; irradiating the resist film with extreme UV of a wavelength of a 1 nm through 30 nm band for pattern exposure; and forming a resist pattern from an unexposed portion of the resist film by developing the resist film after the pattern exposure.
In the first pattern formation method, an adhesion group has a lactone group but has neither a hydroxyl group nor a carboxyl group, and the ring structure of the lactone group has no end and includes no OH group. Therefore, excitation of an OH group at the end of the adhesion group can be avoided in the exposed portion of the resist film subjected to the pattern exposure using the extreme UV, and hence, radicals are minimally generated. Accordingly, since a crosslinking reaction is minimally caused within the base polymer and between polymers, the exposed portion of the resist film can be definitely dissolved in an alkaline developer. As a result, the resist pattern can be formed in a good pattern shape.
In the first pattern formation method, the lactone group is preferably a &ggr;-butyrolactone group, a &dgr;-butyrolactone group, a mevalonic lactone group or an adamantyl lactone group.
Thus, although the exposed portion of the resist film is irradiated with the extreme UV, the excitation of the OH group at the end of the adhesion group can be definitely avoided, so as to definitely improve the solubility of the exposed portion in the alkaline developer.
In the first pattern formation method, the chemically amplified resist material preferably has an aromatic compound that does not generate an acid through irradiation with the extreme UV.
Thus, radicals generated from the base polymer through the extreme UV irradiation and concerned with the crosslinking reaction are captured by the aromatic compound in the exposed portion of the resist film, so that the number of radicals concerned with the crosslinking reaction can be reduced. As a result, the exposed portion of the resist film can be more easily dissolved in the alkaline developer.
In order to solve the problem, the second pattern formation method of this invention comprises the steps of forming a resist film of a chemically amplified resist material including a base polymer, an acid generator for generating an acid through irradiation with light and an aromatic compound that does not generate an acid through irradiation with light; irradiating the resist film with extreme UV of a wavelength of a 1 nm through 30 nm band through a mask for pattern exposure; and forming a resist pattern from an unexposed portion of the resist film by developing the resist film after the pattern exposure.
In the second pattern formation method, although radicals concerned with the crosslinking reaction are generated through the extreme UV irradiation in the exposed portion of the resist film, the radicals are captured by the aromatic compound, and the captured radicals are not diverted to acid generation. Accordingly, the number of radicals generated from the base polymer and concerned with the crosslinking reaction can be reduced, and hence, the crosslinking reaction is minimally caused and the exposed portion of the resist film can be definitely dissolved in an alkaline developer. As a result, the resist pattern can be formed in a good pattern shape.
The aromatic compound included in the chemically amplified resist material used in the first or second pattern formation method is preferably styrene, aniline, methoxybenzene, methoxystyrene, methylstyrene, hydroxybenzene or hydroxystyrene.
Thus, the radicals gen
Endo Masayuki
Sasago Masaru
Chacko-Davis Daborah
Hoff Mark F.
Matsushita Electric Industry Co., Ltd.
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