Radiation imagery chemistry: process – composition – or product th – Diazo reproduction – process – composition – or product – Composition or product which contains radiation sensitive...
Reexamination Certificate
2002-05-28
2004-03-09
Chu, John S. (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Diazo reproduction, process, composition, or product
Composition or product which contains radiation sensitive...
C430S270100, C430S326000, C430S910000
Reexamination Certificate
active
06703178
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a photo resist composition, and particularly to a chemical amplified photoresist composition including polymers, and to a method for lithography to which the photoresist composition is applied.
2. Related Prior Art
Integral circuit layering is crucial in semiconductor industries such that the number of integral layers on an integral circuit must be maximized. Therefore, narrower wire widths for lithography are required. To achieve better resolution, light sources with shorter wavelengths or exposure systems with larger numerical apertures are applied.
Recently, a tetrapolymer iBMA-MMA-tBMA-MMA (poly isobornyl methacrylate-methyl methacrylate-t-butyl methacrylate-methacrylic acid) is reported to be a possible resin system for ArF resist:
For such polymers, there are still some disadvantages, for example, low etch resistance and bad adhesion due to the four monomer composition. Therefore, a new resin for the compositions of resists is eager to be developed.
U.S. Pat. Nos. 6,271,412 and 6,280,898 and Japanese Patent Publication No. 2001-242627 have disclosed different monomers for synthesizing photosensitive polymers, which can form photoresist compositions and then be applied to semiconductor component manufacturing.
The present invention provides a chemical amplified photoresist composition, which comprises a polymer containing a novel lactone alicyclic unit. And the photoresist comprising the polymer provide well-balanced outcome of etching resistance and substrate adhesion.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a chemical amplified photoresist composition, which is suitable for lithography processes and can exhibit excellent resolution, picture sharpness and photosensitivity.
Another object of the present invention is to provide a method for manufacturing semiconductor devices by lithography process, which is particular suitable for ArF, KrF or the like light source and can exhibit excellent resolution, figures and photosensitivity.
Accordingly, the chemical amplified photoresist composition includes a polymer having repeated units of the formula (II),
wherein R
1
is H, haloalkyl group or C
1
-C
4
alkyl group; R
2
is hydroxyl group, C
1
-C
8
alkoxy group or C
1
-C
8
thioalkyl group; G is (CH
2
)
n
, O or S, wherein n is 0, 1, 2, 3 or 4; Rc is a lactone group; and m is 1, 2 or 3.
The chemical amplified photoresist composition can further optionally include a photo-acid generator (PAG), an acid quencher, an additive, a solvent, etc.
The chemical amplified photoresist composition of the present invention can be applied to general lithography processes, and particularly to the process of ArF, KrF or the like light source, whereby excellent resolution, figures and photosensitivity can be achieved. Such processes are well known by those skilled in this art.
The present invention also relates to a method for manufacturing semiconductor devices by lithography, to which the above chemically amplified photoresist composition is applied, and particularly for the exposure process with ArF, KrF or the like light source.
DETAILED DESCRIPTION OF THE INVENTION
The chemical amplified photoresist composition of the present invention includes a polymer having a repeated unit of the formula (II), which is essentially formed through a reaction involving a compound of the following formula (I),
wherein R
1
is H, haloalkyl group or C
1
-C
4
alkyl group; R
2
is hydroxyl group, C
1
-C
8
alkoxy group or C
1
-C
8
thioalkyl group; G is (CH
2
)
n
, O or S, wherein n is 0, 1, 2, 3 or 4; Rc is a lactone group; and m is 1, 2 or 3.
This reaction can be performed by self-polymerization of the above compound or copolymerizing the above compound with other vinyl monomers in the presence of catalysts.
One of the methods for preparing the formula (I) compound is shown below,
wherein R
1
, R
2
and G are defined as the above.
In Step 1, a proper diene compound such as butadiene, cyclopentadiene, furan and thiophene, reacts with maleic anhydride to perform the Diels-Alder reaction. Then, the acid anhydride adducts are reduced under the well-known conditions in the second Step 2. Preferably reaction is carried out using sodium boron hydride in dried polar solvent such as dimethylformamide or tetrahydrofuran. In Step 3, peroxide is provided to oxidize the double-bond compound into an epoxide. In Step 4, the epoxide reacts with a proper nucleophilic reagent such as water, alcohol and thiol, to perform a ring opening addition reaction under an acidic environment and then obtaining a hydroxyl derivative can be obtained. In Step 5, the hydroxyl derivative reacts with (alkyl)acryloyl chloride or acryloyl chloride to perform esterification resulting in and finally the compound of the formula (I) is obtained. Detailed procedures for preparing the compound of the present invention are described in the preferred embodiments.
The compounds of the formula (I) can be polymerized or copolymerized with other vinyl monomers to produce various polymers with or without the assistance of catalysts. Particularly, when being applied to the 193 nm processes, the vinyl monomers preferably have no aryl group to enable the light to pass therethrough. Below are some examples of vinyl monomers, wherein R
3
is H, haloalkyl group, haloalkyl group or C
1
-C
4
alkyl group.
According to the compound of the formula (I), the polymer having a repeated unit of the formula (II) can be synthesized through self-polymerization or copolymerization,
wherein R
1
, R
2
, G, Rc and m are defined as the above.
The structure unit of the polymer or copolymers polymerized or copolymerized from compound (I) can be the following formula (III), formula (IV) or formula (V),
wherein R, R′ and R″ each independently is H, haloalkyl group or methyl group. In the structure unit of formula (III) and (IV) g+h+i=1, more preferably g/(g+h+i)=0.01-0.8, h/(g+h+i)=0.01-0.8, i/(g+h+i)=0.01-0.8; in the structure unit of formula (V) g+h+i+j=1, more preferably g/(g+h+i+j)=0.01-0.5, h/(g+h+i+j)=0.01-0.8, i/(g+h+i+j)=0.01-0.8, j/(g+h+i+j)=0.01-0.8.
The above polymers can be used individually, or by mixing with one or more thereof.
The polymer of the present invention is preferably soluble in organic solvents, and has a glass transfer temperature (Tg) ranging from 50 to 220° C., molecular weight ranging from 1,000 to 500,000, and degradation temperature (Td) greater than 80° C.
The method of polymerization is not restricted, and is preferably done by mixing the above monomers in the existence of catalysts. The catalysts can be those well known by one skilled in this art, and preferably 2,2′-azo-bis-isobutyronitrile (AIBN) or dimethyl-2,2′-azo-bis-isobutyrate radical initiator (V-601).
The chemical amplified photo resist composition of the present invention can further include a photo-acid generator (PAG), an acid quencher, an additive or a solvent.
The above photo-acid generator is not restricted, but can generate acids under ultraviolet or other radiation sources, and be stable before exposure. The preferred photo-acid generators are as follows:
The above photo-acid generators can be used individually, or by mixing with one or more thereof. The photo-acid generator is usually added at 1.0-20 parts per 100 parts of resin in weight, and preferably 0.5-7 parts.
The chemical amplified photoresist composition of the present invention can further include acid quencher to adjust the diffusion of acid. The proper acid quenchers are tetrabutylammonium hydroxide, tetrabutylammonium lactate, tributylamine, trioctylamine, triethanolamine, tris[2-(2-methoxyethoxy)ethyl]amine, N-(2,3-dihydroxypropyl)piperidine, N-(2-hydroxyethyl)piperidine, morpholin, N-(2-hydroxyethyl)morpholin, N-(2-hydroxyethyl)pyrrolidine, N-(2-hydroxyethyl)piperazine, etc. The a
Chen Chi-Sheng
Cheng Meng-Hsum
Li Yen-Cheng
Bacon & Thomas PLLC
Chu John S.
Everlight USA, Inc.
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