Underlayer composition and method of imaging underlayer composition
View Patent ↗A method of forming a pattern comprises diffusing an acid formed by irradiating a portion of a photosensitive layer, into an underlayer comprising an acid sensitive copolymer having acid decomposable groups and attachment groups covalently bonded to the surface of the substrate and/or forming an interpolymer crosslink. Diffusing comprises heating the underlayer and photosensitive layer. The acid sensitive group reacts with the diffused acid to form a polar region on the underlayer, with the shape of the pattern. The photosensitive layer is removed, forming a self-assembling layer comprising a block copolymer having a first block with an affinity for the polar region, and a second block having less affinity for the polar region. The first block forms a domain aligned to the polar region, and the second block forms another domain aligned to the first. Removing either domain exposes a portion of the underlayer.
1. An underlayer comprising:
an acid sensitive copolymer of the formula:
wherein R 1 is a C 1-30 acid decomposable group comprising a tertiary alkyl ester group, an acetal group, a ketal group, a carbonate group, or a combination comprising at least one of the foregoing acid decomposable groups; R 3 is a C 1-30 attachment group comprising a hydroxy group, R 5 and R 7 are independently a C 1-30 functional group comprising an aromatic group or ester group for adjusting neutrality of the acid-sensitive copolymer relative to a self-assembling block copolymer that is to be disposed on the underlayer, where neutrality means that a surface energy of the underlayer is substantially the same as that of at least one block of the block copolymer; R 2 , R 4 , R 6 , and R 8 are independently H or a C 1-10 organic group, mole fractions w and x are 0.001 to 0.999, mole fractions y and z are 0 to 0.9, and the sum of mole fractions w, x, y, and z is 1;
wherein the acid sensitive copolymer is covalently bonded to a hydrophilic surface of a substrate through the attachment group by an alkoxide linkage, or is both covalently bonded to the hydrophilic surface of the substrate through the attachment group by an alkoxide linkage and crosslinked to form an interpolymer crosslink.
2. The underlayer of claim 1 , where the acid decomposable group is a C 4-30 tertiary alkyl ester; wherein the C 4-30 tertiary alkyl comprises a 2-(2-methyl)propyl moiety, a 2-(2-methyl)butyl, 1-methylcyclopentyl moiety, a 1-ethylcyclopentyl moiety, a 1-methylcyclohexyl moiety, a 1-ethylcyclohexyl moiety, a 2-methyladamantyl moiety, a 2-ethyladamantyl moiety, or a combination comprising at least one of the foregoing.
3. The underlayer of claim 1 , where the acid sensitive copolymer has the structure of formula 1:
wherein R 1 is a C 1-30 acid decomposable group comprising a tertiary alkyl ester group, R 3 is a C 1-30 attachment group comprising a hydroxy group, R 5 and R 7 are independently a C 1-30 functional group comprising an aromatic group or an ester group for adjusting neutrality of the acid-sensitive copolymer, where the neutrality is adjusted relative to a block copolymer disposed on the underlayer, R 2 , R 4 , R 6 and R 8 are independently H or a C 1-10 organic group, mole fractions w and x are 0.001 to 0.999 and mole fractions y and z are 0 to less than 0.9, where the sum of mole fractions w, x, y, and z is 1.
4. The underlayer of claim 1 , where the acid sensitive copolymer has the structure of formula 2:
wherein R 9 is a C 1-20 acid decomposable group comprising a tertiary alkyl ester group, R 10 is H, R 2 , R 4 , and R 6 are independently H, methyl, ethyl, or phenyl, mole fraction w is 0.05 to 0.65, mole fraction x is 0.35 to 0.95, and mole fraction y is 0 to 0.9, where the sum of mole fractions x, y, and z is 1.
5. The underlayer of claim 1 , where the acid sensitive copolymer has the structure of formula (3):
where mole fraction a is 0.05 to 0.65, and mole fraction b is 0.35 to 0.95, and the sum of mole fractions a and b is 1.
6. The underlayer of claim 1 , where the acid sensitive copolymer has the structure of formula (4):
where mole fraction a is 0.05 to 0.65, mole fraction b is 0.15 to 0.75, and mole fraction c is 0.20 to 0.80, and the sum of mole fractions a, b, and c is 1.
7. The underlayer of claim 1 , where the acid sensitive copolymer has the structure of formula (5):
where mole fraction a is 0.05 to 0.65, mole fraction b is 0.15 to 0.75, and mole fraction c is 0.20 to 0.80, and the sum of mole fractions a, b, and c is 1.
8. The underlayer of claim 1 , where the acid sensitive copolymer has the structure of formula (6):
wherein R 11 is a C 1-20 acid decomposable group comprising a tertiary alkyl ester group, R 12 is a C 1-30 hydroxy-containing group, R 13 is H, a C 1-10 alkyl, or C 1-10 alkoxy; R 2 , R 4 , and R 6 are independently H, methyl, ethyl, or phenyl, mole fraction x is 0.05 to 0.65, mole fraction y is 0.35 to 0.95, and mole fraction z is 0 to 0.90, where the sum of mole fractions x, y, and z is 1.
9. The underlayer of claim 1 , where the acid sensitive copolymer has the structure of formula (7):
where mole fraction a is 0.05 to 0.65, mole fraction b is 0.15 to 0.75, and mole fraction c is 0.2 to 0.8, and the sum of mole fractions a, b, and c is 1.
10. The underlayer of claim 1 , where the acid sensitive copolymer has the structure of formula (8):
where mole fraction a is 0.05 to 0.65, mole fraction b is 0.15 to 0.75, and mole fraction c is 0.2 to 0.8, and the sum of mole fractions a, b, and c is 1.
11. The underlayer of claim 1 , where the acid sensitive copolymer has the structure of formula (9):
where mole fraction a is 0.05 to 0.65, mole fraction b is 0.15 to 0.75, mole fraction c is 0.2 to 0.8, mole fraction d is 0.1 to 0.6, and the sum of mole fractions a, b, c, and d is 1.