Photoresist polymers of carboxyl-containing alicyclic compounds

Details Photoresist polymers of carboxyl-containing alicyclic compounds Photoresist polymers of carboxyl-containing alicyclic compounds

2001-05-07

2002-04-23

Chu, John S. (Department: 1752)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S283000, C430S270100

Reexamination Certificate

active

06376632

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a carboxyl-containing alicyclic compound as a useful monomer for preparing a photoresist resin and a process for preparing the same. More specifically, the present invention relates to a carboxyl-containing alicyclic compound which is useful as a monomer for synthesizing a photoresist resin for an E-beam (electron-beam), KrF, ArF, an X-ray or EUV which can be applied to a high-density micro-pattern of not more than 0.15 &mgr;m (DRAM of 1 G or more).
BACKGROUND OF THE INVENTION
Most of the conventional ArF photoresist resins have low-etching resistance and insufficient resolution. Physical properties of a photoresist resin are affected by the type of monomers used for preparing the resin, and the production cost of a photoresist resin is very high because of the high price of the monomers used for the resin, so that mass production of the photoresist resin has been restricted. Thus, a lot of attempts have been made to develop the most proper monomer for economically producing a photoresist resin having excellent resolution and etching resistance on a large scale.
SUMMARY OF THE INVENTION
The object of the present invention is to provide photoresist monomers and copolymers which are appropriate for a lithography process using a light source having a short wavelength of not more than 250 nm.
The present invention also provides photoresist compositions comprising said copolymers.
Furthermore, the present invention provides a process for forming a photoresist pattern by using said photoresist composition and a process for preparing a semiconductor element therefrom.
DETAILED DESCRIPTION OF THE INVENTION
Now, the present Invention is described in more detail.
The present inventors have discovered the surprising fact that the alicyclic compounds represented by Chemical Formula 1 below, which have one or more carboxylic groups or tert-butyl groups, are useful as a monomer employed in the synthesis of a photoresist resin for an ArF, EUV, E-beam or X-ray light source. The compounds of the present invention have high purity and low price, so that a photoresist resin of high performance can be economically produced on a large scale therefrom.
[Chemical Formula 1]
In the above formula, R
1
and R
2
, which may be identical to or different from each other, represent hydrogen or a tert-butyl group; X represents hydrogen, hydroxy or oxygen; and n represents a number from 1 to 3.
Furthermore, the present inventors have found that an excellent pattern can be obtained in a lithography process employing a light source of an extremely short wavelength, by using a photoresist composition comprising the compound represented by Chemical Formula 1.
Among the carboxyl-containing alicyclic compounds of the present invention represented by Chemical Formula 1, preferred compounds are listed below:
(a) Compounds of the following formula wherein R
1
and R2 individually represent tert-butyl and X represents oxygen, such as 5-norbornene-2-carbonyl di-tert-butyl malonate; bicyclo[2,2,2]oct-5-ene-2-carbonyl di-tert-butyl malonate; or bicyclo[3,2,2]non-8-ene-2-carbonyl di-tert-butyl malonate:
[Formula 1a]
(b) Compounds of the following formula wherein R
1
is tert-butyl, R
2
is hydrogen and X is oxygen, such as 5-norbornene-2-carbonyl mono-tert-butyl malonate; bicyclo[2,2,2]oct-5-ene-2-carbonyl mono-tert-butyl malonate; or bicyclo[3,2,2]non-8-ene-2-carbonyl mono-tert-butyl malonate:
[Formula 1b]
(c) Compounds of the following formula wherein R
1
and R
2
individually represent hydrogen and X represents oxygen, such as 5-norbornene-2-carbonyl malonic acid; bicyclo[2,2,2]oct-5-ene-2-carbonyl malonic acid; or bicyclo[3,2,2]non-8-ene-2-carbonyl malonic acid:
[Formula 1c]
(d) Compounds of the following formula wherein R
1
and R
2
individually represent tert-butyl and X represents the hydroxy group, such as 5-norbornene-2-yl di-tert-butylhydroxymethyl malonate; bicyclo[2,2,2]oct-5-ene-2-yl di-tert-butylhydroxymethyl malonate; or bicyclo[3,2,2]non-8-ene-2-yl di-tert-butylhydroxymethyl malonate:
[Formula 1d]
(e) Compounds of the following formula wherein R
1
is tert-butyl, R
2
is hydrogen and X is a hydroxy group, such as 5-norbornene-2-yl mono-tert-butylhydroxymethyl malonate; bicyclo[2,2,2]oct-5-ene-2-yl mono-tert-butylhydroxymethyl malonate; or bicyclo[3,2,2]non-8-ene-2-yl mono-tert-butylhydroxymethyl malonate:
[Formula 1e]
(f) Compounds of the following formula wherein R
1
and R
2
individually represent hydrogen and X represents a hydroxy group, such as 5-norbornene-2-yl hydroxymethylmalonic acid; bicyclo[2,2,2]oct-5-ene-2-yl hydroxymethylmalonic acid; or bicyclo[3,2,2]non-8-ene-2-yl hydroxymethylmalonic acid:
[Formula 1f]
(g) Compounds of the following formula wherein R
1
and R
2
individually represent tert-butyl and X represents hydrogen, such as 5-norbornene-2-yl di-tert-butylmethyl malonate; bicyclo[2,2,2]oct-5-ene-2-yl di-tert-butylmethyl malonate; or bicyclo[3,2,2]non-8-ene-2-yl di-tert-butylmethyl malonate:
[Formula 1g]
(h) Compounds of the following formula wherein R
1
is tert-butyl, R
2
is hydrogen and X is hydrogen, such as 5-norbornene-2-yl mono-tert-butylmethyl malonate; bicyclo[2,2,2]oct-5-ene-2-yl mono-tert-butylmethyl malonate; or bicyclo[3,2,2]non-8-ene-2-yl mono-tert-butylmethyl malonate:
[Formula 1h]
(i) Compounds of the following formula wherein R
1
, R
2
and X individually represent hydrogen, such as 5-norbornene-2-yl methylmalonic acid; bicyclo[2,2,2]oct-5-ene-2-yl methylmalonic acid; or bicyclo[3,2,2]non-8-ene-2-yl methyl malonic acid.
[Formula 1i]
The carboxyl-containing alicyclic compound of the present invention, represented by Chemical Formula 1, can be prepared by reacting a compound represented by Chemical Formula 2 below with a malonate represented by Chemical Formula 3:
R
4
O
2
C—C
⊖
HNa
⊖
—CO
2
R
5
in the presence of a solvent such as tetrahydrofuran (THF), dimethylformamide (DMF) or dioxane.
[Chemical Formula 2]
In Formula 2 above, R
3
represents hydrogen, or halogen such as chloro, bromo and iodo, Y represents hydrogen or oxygen, n is a number from 1 to 3, and R
4
and R
5
, which may be identical to or different from each other, represent the tert-butyl group or a sodium ion.
The compound represented by Chemical Formula 2, which is used as a starting material in the present invention can be prepared as follows:
The alicyclic compound of Chemical Formula 2 wherein R
3
is hydrogen or halogen and Y is oxygen, is prepared by reacting 1,3-cyclopentadiene, 1,3-cyclohexadiene or 1,3-cycloheptadiene with acroyl halide or acrolein at a temperature between −40° C. to 80° C., preferably between −20° C. to 30° C. in an equivalent ratio of 1:1, as shown in the following Reaction Scheme A:
[Reaction Scheme A]
The alicyclic compound of Chemical Formula 2 wherein R
3
is a halogen such as bromo, chloro or iodo and Y is hydrogen, is prepared by reacting 5-norbornene-2-methanol, [2,2,2]bicyclooctene-2-methanol or [3,2,2]bicyclononene-6-methanol with some excess of thionyl chloride (1.2 equiv.) at a temperature between −40° C. to 80° C., preferably between 0° C. to 25° C., as shown in the following reaction scheme B:
[Reaction Scheme B]
The malonic acid compounds of the present invention, represented by Chemical Formula 3, include:
sodium salt of di-tert-butyl malonate;
(CH
3
)
3
CO
2
C—C
⊖
HNa
⊕
—CO
2
C(CH
3
)
3
sodium salt of mono-tert-butyl malonate;
Na
⊕⊖
O
2
C—C
⊖
HNa
⊕
—CO
2
C(CH
3
)
3
sodium malonate;
Na
⊕⊖
O
2
C—C
⊖
HNa
⊕
—CO
2
⊖
Na
⊕
In the process according to the present invention, the compound of Chemical Formula 2 and malonate salt of Chemical Formula 3 are preferably reacted in a mola

Affiliated with

Also associated with

Rating

Photoresist polymers of carboxyl-containing alicyclic compounds does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Photoresist polymers of carboxyl-containing alicyclic compounds, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Photoresist polymers of carboxyl-containing alicyclic compounds will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2862875