Graded topcoat materials for immersion lithography

A composition, comprising:

• a mixture of a first polymer and a second polymer, said first polymer containing fluorine, said second polymer miscible with said first polymer, said second polymer different from said first polymer, a weight percentage of fluorine in said first polymer greater than a weight percentage of fluorine in said second polymer;
• a casting solvent;
• said first polymer comprising one or more different monomers selected from the group consisting of:
• wherein each Z1, Z2, and Z3 is independently selected from the group consisting of linear alkylenes, branched alkylenes, cyclic alkylenes, polycyclic alkylenes, linear heteroalkylenes, branched heteroalkylenes, cyclic heteroalkylenes, polycyclic heteroalkylenes, ester groups, carbonyl groups, carbonate groups, acetal groups, ketal groups, siloxyl groups, carboxylic acid groups, carboxylic acid anhydride groups, carboxylic acid anhydride half-ester groups, ether groups, amide groups, carbamate groups, thioether groups, fluorinated linear alkylenes, fluorinated branched alkylenes, fluorinated cyclic alkylenes, polycyclic alkylenes, fluorinated linear heteroalkylenes, fluorinated branched heteroalkylenes, fluorinated cyclic heteroalkylenes, fluorinated polycyclic heteroalkylenes, fluorinated ester groups, fluorinated carbonyl groups, fluorinated carbonate groups, fluorinated acetal groups, fluorinated ketal groups, fluorinated siloxyl groups, fluorinated carboxylic acid groups, fluorinated carboxylic acid anhydride groups, fluorinated carboxylic acid anhydride half-ester groups, fluorinated ether groups, fluorinated amide groups, fluorinated carbamate groups, and fluorinated thioether groups;
• wherein R1 is selected from the group consisting of a fluoroalcohol group, a fluoroalcohol group protected with an acid-labile group, a fluoroalcohol group protected with a base-labile group, a fluoroalcohol group protected with an acid-labile fluorinated group, a fluoroalcohol group protected with a base-labile fluorinated group, and an —X1—Y1 group wherein X1 is selected from the group consisting of linear alkylenes, branched alkylenes, cyclic alkylenes, polycyclic alkylenes, linear heteroalkylenes, branched heteroalkylenes, cyclic heteroalkylenes, polycylic heteroalkylenes, ester groups, carbonyl groups, amide groups, ether groups, thioether groups, carbonate groups, carbamate groups, acetal groups, ketal groups and Y1 is selected from the group consisting of a fluoroalcohol group, a fluoroalcohol group protected with an acid-labile group, a fluoroalcohol group protected with a base-labile group, a fluoroalcohol group protected with an acid-labile fluorinated group, and a fluoroalcohol group protected with a base-labile fluorinated group;
• wherein R2 is selected from the group consisting of hydrogen, fluorine, a fluoroalcohol group, a sulfonamide group, a phenolic group, a naphtholic group, a carboxylic acid group and a sulfonic acid group and an —X2—Y2 group wherein X2 is selected from the group consisting of linear alkylenes, branched alkylenes, cyclic alkylenes, polycyclic alkylenes, linear heteroalkylenes, branched heteroalkylenes, cyclic heteroalkylenes, polycylic heteroalkylenes, ester groups, carbonyl groups amide groups, ether groups, thioether groups, carbonate groups, carbamate groups, acetal groups, ketal groups and Y2 is selected from the group consisting of a fluoroalcohol group, a sulfonamide group, a phenolic group, a naphtholic group, a carboxylic acid group and a sulfonic acid group;
• wherein R3 is selected from the group consisting of hydrogen, fluorine, an acid-labile group, a base-labile group, an acid-labile fluorinated group, a base-labile fluorinated group, linear alkanes, branched alkanes, cyclic alkanes, polycyclic alkanes, linear heteroalkanes, branched heteroalkanes, cyclic heteroalkanes, polycylic heteroalkanes, fluorinated linear alkanes, fluorinated branched alkanes, fluorinated cyclic alkanes, fluorinated polycyclic alkanes, fluorinated linear heteroalkanes, fluorinated branched heteroalkanes, fluorinated cyclic heteroalkanes, fluorinated polycylic heteroalkanes and an —X3—Y3 group wherein X3 is selected from the group consisting of linear alkylenes, branched alkylenes, cyclic alkylenes, polycyclic alkylenes, linear heteroalkylenes, branched heteroalkylenes, cyclic heteroalkylenes, polycylic heteroalkylenes, ester groups, carbonyl groups, amide groups, ether groups, thioether groups, carbonate groups, carbamate groups, acetal groups, ketal groups and Y3 is selected from the group consisting of hydrogen, fluorine, an acid-labile group, a base-labile group, an acid-labile fluorinated group, a base-labile fluorinated group, linear alkanes, branched alkanes, cyclic alkanes, polycyclic alkanes, linear heteroalkanes, branched heteroalkanes, cyclic heteroalkanes, polycylic heteroalkanes, fluorinated linear alkanes, fluorinated branched alkanes, fluorinated cyclic alkanes, fluorinated polycyclic alkanes, fluorinated linear heteroalkanes, fluorinated branched heteroalkanes, fluorinated cyclic heteroalkanes, fluorinated polycylic heteroalkanes;
• and
• said second polymer comprising one or more different monomers selected from the group consisting of:
• wherein each Z4, Z5, and Z6 is independently selected from the group consisting of linear alkylenes, branched alkylenes, cyclic alkylenes, polycyclic alkylenes, linear heteroalkylenes, branched heteroalkylenes, cyclic heteroalkylenes, polycyclic heteroalkylenes, ester groups, carbonyl groups, carbonate groups, acetal groups, ketal groups, siloxyl groups, carboxylic acid groups, carboxylic acid anhydride groups, carboxylic acid anhydride half-ester groups, ether groups, amide groups, carbamate groups, thioether groups, fluorinated linear alkylenes, fluorinated branched alkylenes, fluorinated cyclic alkylenes, polycyclic alkylenes, fluorinated linear heteroalkylenes, fluorinated branched heteroalkylenes, fluorinated cyclic heteroalkylenes, fluorinated polycyclic heteroalkylenes, fluorinated ester groups, fluorinated carbonyl groups, fluorinated carbonate groups, fluorinated acetal groups, fluorinated ketal groups, fluorinated siloxyl groups, fluorinated carboxylic acid groups, fluorinated carboxylic acid anhydride groups, fluorinated carboxylic acid anhydride half-ester groups, fluorinated ether groups, fluorinated amide groups, fluorinated carbamate groups, and fluorinated thioether groups;
• wherein R4 is selected from the group consisting of a sulfonic acid group, a sulfinic acid group, a carboxylic acid group and an —X4—Y4 group wherein X4 is selected from the group consisting of linear alkylenes, branched alkylenes, cyclic alkylenes, polycyclic alkylenes, linear heteroalkylenes, branched heteroalkylenes, cyclic heteroalkylenes, polycylic heteroalkylenes, ester groups, carbonyl groups, amide groups, ether groups, thioether groups, carbonate groups, carbamate groups, acetal groups, ketal groups and Y4 is selected from the group consisting of a sulfonic acid group, a sulfinic acid group, and a carboxylic acid group;
• wherein R5 is selected from the group consisting of hydrogen, fluorine, a fluoroalcohol group, a sulfonamide group, a phenolic group, a naphtholic group, a carboxylic acid group and a sulfonic acid group and an —X5—Y5 group wherein X5 is selected from the group consisting of linear alkylenes, branched alkylenes, cyclic alkylenes, polycyclic alkylenes, linear heteroalkylenes, branched heteroalkylenes, cyclic heteroalkylenes, polycylic heteroalkylenes, ester groups, carbonyl groups, amide groups, ether groups, thioether groups, carbonate groups, carbamate groups, acetal groups, ketal groups and Y5 is selected from the group consisting of a fluoroalcohol group, a sulfonamide group, a phenolic group, a naphtholic group, a carboxylic acid group and a sulfonic acid group;
• and
• wherein R6 is selected from the group consisting of hydrogen, fluorine, an acid-labile group, a base-labile group, an acid-labile fluorinated group, a base-labile fluorinated group, linear alkanes, branched alkanes, cyclic alkanes, polycyclic alkanes, linear heteroalkanes, branched heteroalkanes, cyclic heteroalkanes, polycylic heteroalkanes, fluorinated linear alkanes, fluorinated branched alkanes, fluorinated cyclic alkanes, fluorinated polycyclic alkanes, fluorinated linear heteroalkanes, fluorinated branched heteroalkanes, fluorinated cyclic heteroalkanes, fluorinated polycylic heteroalkanes and an —X6—Y6 group wherein X6 is selected from the group consisting of linear alkylenes, branched alkylenes, cyclic alkylenes, polycyclic alkylenes, linear heteroalkylenes, branched heteroalkylenes, cyclic heteroalkylenes, polycylic heteroalkylenes, ester groups, carbonyl groups, amide groups, ether groups, thioether groups, carbonate groups, carbamate groups, acetal groups, ketal groups and Y6 is selected from the group consisting of hydrogen, fluorine, an acid-labile group, a base-labile group, an acid-labile fluorinated group, a base-labile fluorinated group, linear alkanes, branched alkanes, cyclic alkanes, polycyclic alkanes, linear heteroalkanes, branched heteroalkanes, cyclic heteroalkanes, polycylic heteroalkanes, fluorinated linear alkanes, fluorinated branched alkanes, fluorinated cyclic alkanes, fluorinated polycyclic alkanes, fluorinated linear heteroalkanes, fluorinated branched heteroalkanes, fluorinated cyclic heteroalkanes, fluorinated polycylic heteroalkanes.