초록 ▼

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-crosslinke

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: R1 is chosen from hydrogen, fluorine, C1-C3 alkyl and C1-C3 fluoroalkyl; and Ar1 is an optionally substituted aryl group that is free of crosslinkable groups; and a second unit of the following general formula (II): wherein: R3 is chosen from hydrogen, fluorine, C1-C3 alkyl and C1-C3 fluoroalkyl; and R4 is chosen from optionally substituted C1 to C12 linear, branched or cyclic alkyl, and optionally substituted C6 to C15 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.

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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-cros

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: R1 is chosen from hydrogen, fluorine, C1-C3 alkyl and C1-C3 fluoroalkyl; and Ar1 is an optionally substituted aryl group that is free of crosslinkable groups; and a second unit of the following general formula (II): wherein: R3 is chosen from hydrogen, fluorine, C1-C3 alkyl and C1-C3 fluoroalkyl; and R4 is chosen from optionally substituted C1 to C12 linear, branched or cyclic alkyl, and optionally substituted C6 to C15 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: R1 is chosen from hydrogen, fluorine, C1-C3 alkyl and C1-C3 fluoroalkyl; R2 is independently chosen from halogen, nitro, cyano, and optionally substituted C1-C15 linear, branched or cyclic alkyl, alkenyl, alkynyl, C6-C18 aryl, and combinations thereof, and R2 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: R1 is chosen from hydrogen, fluorine, C1-C3 alkyl and C1-C3 fluoroalkyl; and Ar1 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: R1 is chosen from hydrogen, fluorine, C1-C3 alkyl and C1-C3 fluoroalkyl; R2 is independently chosen from halogen, nitro, cyano, and optionally substituted C1-C15 linear, branched or cyclic alkyl, alkenyl, alkynyl, C6-C18 aryl, and combinations thereof, and R2 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.