For getting information about the distribution of chemical composition, several model polymers were prepared under
different polymerization conditions and were measured by critical adsorption point-liquid chromatography (CAP-LC).
In the copolymer system of 8- and 9- (4-oxatricyclo[5.2.1.02,6]decane-3-one) acrylate (OTDA) and 2-ethyl-2-adamantyl
methacrylate (EAdMA), the peak shapes of the CAP-LC chromatogram varied according to the polymerization condition
although they indicated same molecular weight and averaged chemical composition. The difference of the CAP-LC
elution curves was related to the chemical composition distribution of copolymers for CAP-LC measurement combined
with proton nuclear magnetic resonance (1H-NMR). The terpolymers consisted of α-hydroxy-γ-butyrolactone
methacrylate (GBLMA), 2-methyl-2-adamantyl methacrylate (MAdMA) and 1-hydroxy-3-adamantyl methacrylate
(HAdMA) were prepared under various polymerization conditions. In the terpolymer system that had same molecular
weight and average chemical composition, the solubility parameter (&dgr;) and the dissolution rate were measured. The &dgr;
value and the dissolution rate curve were different among these terpolymers. It was suggested that the &dgr; value and the
chemical composition distribution of these terpolymers have a significant influence on the lithographic performance.
KEYWORDS: Polymers, Lithography, Hydrogen, Line edge roughness, Etching, Polymerization, Immersion lithography, Resistance, Transmittance, Chemical species
Design and development of novel monomers and copolymers for 193-nm lithography are described. At the present time, 193-nm lithography is required for 65-nm node and below. Novel monomers and copolymers are considered to be candidates for the development of higher performance resist materials. We focused our attention on pattern profile and line edge roughness. In design of novel monomers, molecular orbital calculation was adopted. It was revealed that CN-group has a higher potential than other polar groups. Novel monomers that contain CN-group were designed, synthesized and co-polymerized with traditional acrylate monomers. It is expected that these copolymers could be higher performance resist materials that could be used in 65-nm node and below.
We have developed novel acrylic copolymers for ArF photoresist which have more etching durability than usual. The excellent one of those copolymers in handling contains 8- or 9- methacryloyloxy-4-oxatricyclo[5.2.1.02,6]decan-3-one (OTDMA) and (gamma) ,(gamma) -dimethyl-(alpha) -methylene-(gamma) -butyrolac tone (DMMB). OTDMA is a new methacrylic ester monomer having a lactone unit with bridged structure. DMMB introduces a lactone structure to the main chain of acrylic copolymers. It was suggested that the solubility of monomers depends on the hindrance of their polar group, and the role of the hydrophilic monomers has been discussed from the standpoint of the position of their hydrophilic parts.
The relationship between the sensitivity of ArF photoresist and the end group structures of copolymers consisting of (beta) -hydroxy-(gamma) -butyrolactone methacrylate (HGBMA) and 2-methyl-2-adamantyl methacrylate (MadMA) was investigated. The sensitivity is strongly dependent on the kind and amount of end groups. It has been found that the copolymer with relatively non-polar end group structure has higher sensitivity than that with polar end group structure, and that the sensitivity of copolymer with end groups of methylisobutyrate and 1-octhylthio moieties showed approximately three times higher than that of copolymer with end groups of isobutyronitrile and 2-hydroxyethylthio moieties. The difference of sensitivity among these copolymers has been discussed from the view point of the change of development rate attributed to the amount of carboxylic acid groups formed in the resist film by exposure of 193nm light.
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