Fluoro-containing photosensitive polymer and photoresist...

Details Fluoro-containing photosensitive polymer and photoresist... Fluoro-containing photosensitive polymer and photoresist...

2001-09-06

2003-09-30

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

C430S907000, C526S242000, C526S247000, C526S270000, C526S281000

Reexamination Certificate

active

06627382

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a photoresist composition, and more particularly, to a photoresist composition comprising fluoro-containing polymer.
2. Description of the Related Art
As the manufacture of semiconductor devices becomes more complex and semiconductor chips are more integrated, it is essential to form fine patterns in photolithography. Furthermore, as the capacity of a semiconductor memory device increases to exceed 4 Gigabit, a pattern size having a design rule less than 0.1 &mgr;m is required. Accordingly, there are limitations to using a KrF excimer laser (248 nm wavelength) or an ArF excimer laser (193 nm wavelength) as the light source in photolithography. Thus, a new laser referred to as a “F
2
excimer laser (157 nm wavelength)” has been introduced.
In general, a photosensitive polymer is used as photoresist material for the F
2
excimer laser. The photoresist material should have characteristics of: (1) being transparent against 157 nm wavelength, (2) having high resistance to dry etching, (3) having excellent adhesion to a underlying layer and (4) being capable of being easily developed using a developer such as tetramethyl ammonium hydroxide (TMAH), which is very common in semiconductor manufacturing.
However, conventional photosensitive polymers have poor optical transparency at 157 nm wavelength. When the conventional photosensitive polymer is used for the photoresist material layer, the photoresist material is formed on an underlying layer with thickness of about 1,000 Å, which is a much thinner thickness than normal thickness of the photoresist material. In this case, the photoresist material layer displays inadequate etch resistance and in some cases, can be defective because of a thinner thickness layer.
Thus, much research has been devoted to a photosensitive polymer suitable for use with a F
2
excimer laser (157 nm wavelength), in which a fluorine is introduced to a photosensitive polymer. This polymer may be represented by the following chemical formula:
The photosensitive polymer having maleic anhydride such as Chemical formula 1, may be easily made into a radical polymerization, and can improve on the adhesion characteristics with respect to an underlying layer. However, the photoresist material having maleic anhydride has poor optical transparency. The photoresist material having Chemical formula 2 has better optical transparency than the photoresist material having Chemical 1, but it has poor adhesion to an underlying layer because of hydrophobic characteristic.
Accordingly, it would be desirable to develop new photoresist materials, which have: (1) high optical transparent at a wavelength of 157 nm; (2) strong resistance to dry etching; and (3) excellent adhesiveness to a underlying layer.
SUMMARY OF THE INVENTION
A photosensitive polymer is provided which comprises: (a) perfluoro-2,2-dimethy-1,3-dioxol derivatives having the following repeating unit:
and (b) vinyl derivatives having the following repeating unit:
wherein R
1
is H, Cl, or F; each of R
2
and R
3
is H or F; R
4
is H, F, CF
3
, OCF
3
, OCF
2
CF
3
, OCF
2
CF
2
CF
3
, CH
2
C(CF
3
)
2
OH, fluorinated alkyloxy group having an acid-labile group, n-perfluoroalkyl group having 1 to 8 carbon atoms, OR
F
(wherein R
F
is n-perfluoroalkyl group having 1 to 3 carbon atoms), or OQZ (wherein Q is perfluorinated alkylene group having 0 to 5 oxygen atoms, the sum of carbon atom and oxygen atom in the Q is 2 to 10, and Z is COOR, SO
2
F, CN, COF, or OCH
3
, wherein R is alkyl group having 1 to 4 carbon).
According to the preferred embodiment of the present invention, R
4
is CH
2
C(CF
3
)
2
OCH
2
OCH
3
, CH
2
C(CF
3
)
2
OCH
2
OCH
2
CH
3
, CH
2
C(CF
3
)
2
OCH(CH
3
)OCH
3
, or CH
2
C(CF
3
)
2
OCH(CH
3
)OCH
2
CH
3
, the photosensitive polymer has a weight average molecular weight ranging from about 3,000 to about 200,000. Preferably, the photosensitive polymer has a weight average molecular weight ranging from about 4,000 to about 50,000.
A photosensitive polymer is provided which comprises: (a) perfluoro-2,2-dimethy-1,3-dioxol derivative having the following repeating unit:
and (b) norbornen derivative having the following repeating unit:
wherein R
9
is H, F, CF
3
, OCF
3
, OCF
2
CF
3
, OCF
2
CF
2
CF
3
, CH
2
C(CF
3
)
2
OH, fluorinated alkyloxy group having an acid-labile group, n-perfluoroalkyl group having 1 to 8 carbon atoms, OR
F
(wherein R
F
is n-perfluoroalkyl group having 1 to 3 carbon atoms), or OQZ (wherein Q is perfluorinated alkylene group having 0 to 5 oxygen atoms, the sum of carbon atom and oxygen atom in the Q is 2 to 10, and Z is COOR, SO
2
F, CN, COF, or OCH
3
, wherein R is alkyl group having 1 to 4 carbon).
According to a preferred embodiment of the present invention, R
9
is CH
2
C(CF
3
)
2
OCH
2
OCH
3
, CH
2
C(CF
3
)
2
OCH
2
OCH
2
CH
3
, CH
2
C(CF
3
)
2
OCH(CH
3
)OCH
3
, or CH
2
C(CF
3
)
2
OCH(CH
3
)OCH
2
CH
3
. The photosensitive polymer has a weight average molecular weight ranging from about 3,000 to about 200,000. Preferably, the photosensitive polymer has a weight average molecular weight ranging from about 4,000 to about 50,000.
A photosensitive polymer is provided which comprises: (a) perfluoro-2,2-dimethy-1,3-dioxol derivative having the following repeating unit:
(b) vinyl derivative having the following repeating unit:
and (c) norbornen derivative having the following repeating unit:
wherein R
1
is H, Cl, or F; each of R
2
and R
3
is H or F; each of R
4
and R
9
is H, F, CF
3
, OCF
3
, OCF
2
CF
3
, OCF
2
CF
2
CF
3
, CH
2
C(CF
3
)
2
OH, fluorinated alkyloxy group having an acid-labile group, n-perfluoroalkyl group having 1 to 8 carbon atoms, OR
F
(wherein R
F
is n-perfluoroalkyl group having 1 to 3 carbon atoms), or OQZ (wherein Q includes perfluorinated alkylene group having 0 to 5 oxygen atoms, the sum of carbon atom and oxygen atom in the Q is 2 to 10, and Z is COOR, SO
2
F, CN, COF, or OCH
3
, wherein R is alkyl group having 1 to 4 carbon).
According to a preferred embodiment of the present invention, at least one of R
4
and R
9
is CH
2
C(CF
3
)
2
OCH
2
OCH
3
, CH
2
C(CF
3
)
2
OCH
2
OCH
2
CH
3
, CH
2
C(CF
3
)
2
OCH(CH
3
)OCH
3
, or CH
2
C(CF
3
)
2
OCH(CH
3
)OCH
2
CH
3
. The photosensitive polymer has a weight average molecular weight ranging from about 3,000 to about 200,000. Preferably, the photosensitive polymer has a weight average molecular weight ranging from about 4,000 to about 50,000.
A photoresist compostion is also provided which comprises: (a) a photosensitive polymer comprsing: (a-1) perfluoro-2,2-dimethy-1,3-dioxol derivatives having the following repeating unit:
and (a-2) at least one comonomer of a vinyl derivative having the following repeating unit:
and a norbornen derivative having the following repeating unit:
and (b) a photoacid generator (PAG),
wherein R
1
is H, Cl, or F; each of R
2
and R
3
is H or F; each of R
4
and R
9
is H, F, CF
3
, OCF
3
, OCF
2
CF
3
, OCF
2
CF
2
CF
3
, CH
2
C(CF
3
)
2
OH, fluorinated alkyloxy group having an acid-labile group, n-perfluoroalkyl group having 1 to 8 carbon atoms, OR
F
(wherein R
F
is n-perfluoroalkyl group having 1 to 3 carbon atoms), or OQZ (wherein Q is perfluorinated alkylene group having 0 to 5 oxygen atoms, the sum of carbon atom and oxygen atom in the Q is 2 to 10, and Z is COOR, SO
2
F, CN, COF, or OCH
3
, wherein R is alkyl group having 1 to 4 carbon).
According to the preferred embodiment of the present invention, at least one of R
4
and R
9
is CH
2
C(CF
3
)
2
OCH
2
OCH
3
, CH
2
C(CF
3
)
2
OCH
2
OCH
2
CH
3
, CH
2
C(CF
3
)
2
OCH(CH
3
)OCH
3
, or CH
2
C(CF
3
)
2
OCH(CH
3
)OCH
2
CH
3
.
According to an aspect of the invention, the photoresist composition includes from about 0.5 to about 20 weight percent of the photoacid generator based on the weight of the photosensitive polymer, and the photoacid generator is selected from the group consisting of triarylsulfonium salt, diaryliodonium salt, sulfonate, and the mixtures thereof.
According to an aspect of the invention, the photoresist composition furthe

Affiliated with

Also associated with

Rating

Fluoro-containing photosensitive polymer and photoresist... does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Fluoro-containing photosensitive polymer and photoresist..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Fluoro-containing photosensitive polymer and photoresist... will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-3104808