Gap-fill methods
View Patent ↗Gap-fill methods comprise: (a) providing a semiconductor substrate having a relief image on a surface of the substrate, the relief image comprising a plurality of gaps to be filled; (b) applying a gap-fill composition over the relief image, wherein the gap-fill composition comprises a non-crosslinked crosslinkable polymer, an acid catalyst, a crosslinker and a solvent, wherein the crosslinkable polymer comprises a first unit of the following general formula (I): wherein: R 1 is chosen from hydrogen, fluorine, C 1 -C 3 alkyl and C 1 -C 3 fluoroalkyl; and Ar 1 is an optionally substituted aryl group that is free of crosslinkable groups; and a second unit of the following general formula (II): wherein: R 3 is chosen from hydrogen, fluorine, C 1 -C 3 alkyl and C 1 -C 3 fluoroalkyl; and R 4 is chosen from optionally substituted C 1 to C 12 linear, branched or cyclic alkyl, and optionally substituted C 6 to C 15 aryl, optionally containing heteroatoms, wherein at least one hydrogen atom is substituted with a functional group independently chosen from hydroxyl, carboxyl, thiol, amine, epoxy, alkoxy, amide and vinyl groups; and (c) heating the gap-fill composition at a temperature to cause the polymer to crosslink. The methods find particular applicability in the manufacture of semiconductor devices for the filling of high aspect ratio gaps.
1. A gap-fill method, comprising:
(a) providing a semiconductor substrate having a relief image on a surface of the substrate, the relief image comprising a plurality of gaps to be filled;
(b) applying a gap-fill composition over the relief image, wherein the gap-fill composition comprises a non-crosslinked crosslinkable polymer, an acid catalyst, a crosslinker and a solvent, wherein the crosslinkable polymer comprises a first unit of the following general formula (I):
wherein: R 1 is chosen from hydrogen, fluorine, C 1 -C 3 alkyl and C 1 -C 3 fluoroalkyl; and Ar 1 is an optionally substituted aryl group that is free of crosslinkable groups; and a second unit of the following general formula (II):
wherein: R 3 is chosen from hydrogen, fluorine, C 1 -C 3 alkyl and C 1 -C 3 fluoroalkyl; and R 4 is chosen from optionally substituted C 1 to C 12 linear, branched or cyclic alkyl, and optionally substituted C 6 to C 15 aryl, optionally containing heteroatoms, wherein at least one hydrogen atom is substituted with a functional group independently chosen from hydroxyl, carboxyl, thiol, amine, amide and vinyl groups; and
(c) heating the gap-fill composition at a temperature to cause the polymer to crosslink.
2. The method of claim 1 , wherein the first unit is chosen from one or more unit chosen from the following formula (I-A), (I-B) and (1-C):
wherein: R 1 is chosen from hydrogen, fluorine, C 1 -C 3 alkyl and C 1 -C 3 fluoroalkyl; R 2 is independently chosen from halogen, nitro, cyano, and optionally substituted C 1 -C 15 linear, branched or cyclic alkyl, alkenyl, alkynyl, C 6 -C 18 aryl, and combinations thereof, and R 2 is free of crosslinkable groups; a is an integer from 0 to 5; b is an integer from 0 to 7; and c is an integer from 0 to 9.
3. The method of claim 2 , wherein the first unit is:
4. The method of claim 1 , wherein the second unit is chosen from one or more of the following units:
5. The method of claim 4 , wherein the second unit is:
6. The method of claim 1 , wherein the crosslinkable polymer consists of the units of general formula (I) and general formula (II).
7. The method of claim 1 , wherein the crosslinkable polymer has a weight average molecular weight of greater than 9000.
8. The method of claim 1 , wherein the gaps have a width of less than 50 nm and an aspect ratio of 2 or more.
9. The method of claim 1 , further comprising prior to causing the gap fill composition to crosslink, heating the gap-fill composition at a temperature to cause the gap-fill composition to fill the plurality of gaps.
10. The method of claim 9 , wherein the heating to fill the plurality of gaps and the heating to crosslink are conducted in a single process.
11. A gap-fill method, comprising:
(a) providing a semiconductor substrate having a relief image on a surface of the substrate, the relief image comprising a plurality of gaps to be filled;
(b) applying a gap-fill composition over the relief image, wherein the gap-fill composition comprises a non-crosslinked crosslinkable polymer, an acid catalyst, a crosslinker and a solvent, wherein the crosslinkable polymer comprises a first unit of the following general formula (I):
wherein: R 1 is chosen from hydrogen, fluorine, C 1 -C 3 alkyl and C 1 -C 3 fluoroalkyl; and Ar 1 is an optionally substituted aryl group that is free of crosslinkable groups; and a second unit chosen from the following:
(c) heating the gap-fill composition at a temperature to cause the polymer to crosslink.
12. The method of claim 11 , wherein the first unit is chosen from one or more unit chosen from the following formula (I-A), (I-B) and (1-C):
wherein: R 1 is chosen from hydrogen, fluorine, C 1 -C 3 alkyl and C 1 -C 3 fluoroalkyl; R 2 is independently chosen from halogen, nitro, cyano, and optionally substituted C 1 -C 15 linear, branched or cyclic alkyl, alkenyl, alkynyl, C 6 -C 18 aryl, and combinations thereof, and R 2 is free of crosslinkable groups; a is an integer from 0 to 5; b is an integer from 0 to 7; and c is an integer from 0 to 9.
13. The method of claim 12 , wherein the first unit is:
14. The method of claim 11 , wherein the crosslinkable polymer consists of the units of general formula (I) and of the second unit.
15. The method of claim 11 , wherein the crosslinkable polymer has a weight average molecular weight of greater than 9000.
16. The method of claim 11 , wherein the gaps have a width of less than 50 nm and an aspect ratio of 2 or more.
17. The method of claim 11 , further comprising prior to causing the gap fill composition to crosslink, heating the gap-fill composition at a temperature to cause the gap-fill composition to fill the plurality of gaps.
18. The method of claim 17 , wherein the heating to fill the plurality of gaps and the heating to crosslink are conducted in a single process.