Compositions and methods for selectively etching silicon nitride films
The invention relates to compositions and methods for the selective wet etching of a surface of a microelectronic device that contains both silicon nitride (SiN) and polysilicon. An etching composition as described comprises phosphoric acid, certain polysilicon corrosion inhibitors, along with certain silanes. The combination of the two components was found to greatly improve the selectivity of the silicon nitride etching composition in the presence of polysilicon.
1. A composition comprising: concentrated phosphoric acid, in an amount of at least 60 weight percent, based on the total weight of the composition; a compound chosen from linear and branched C 8 -C 16 alkylbenzenesulfonic acids and C 6 -C 12 alkyldiphenyl oxide disulfonic acids; and a compound of the formula Si[phenyl-(—CH 2 —) x ] n (OR) m , wherein n is 1, 2, or 3, m is 1, 2, or 3, and the sum of n and m is 4, and x is 0, 1, 2 or 3, and wherein each R is independently chosen from C 1 -C 4 alkyl.
2. The composition of claim 1 , wherein each R is methyl.
3. The composition of claim 1 , wherein n is 1.
4. The composition of claim 1 , wherein the compound chosen from linear and branched C 8 -C 16 alkylbenzenesulfonic acids and C 6 -C 12 alkyldiphenyl oxide disulfonic acids is chosen from
hexyl diphenyl oxide disulfonic acid;
tetrapropyl-(sulfophenoxy)-benzenesulfonic acid;
dodecylbenzenesulfonic acid; and
4-octylbenzenesulfonic acid.
5. The composition of claim 1 , further comprising added silica.
6. The composition of claim 1 , further comprising at least one silane chosen from (a) alkylamino alkoxysilanes and (b) alkylamino hydroxyl silanes, wherein the silane possesses at least one moiety chosen from alkoxy and hydroxyl.
7. The composition of claim 1 , further comprising a compound chosen from
N-(3-trimethoxysilylpropyl)diethylenetriamine;
N-(2-aminoethyl)-3-aminopropyltriethoxy silane;
N-(2-aminoethyl)-3-aminopropyl silane triol;
N 1 -(3-trimethoxysilylpropyl)diethylenetriamine;
N-(6-aminohexyl)aminopropyltrimethoxysilane;
(3-aminopropyl)triethoxy-silane; and
(3-aminopropyl)silane triol.
8. The composition of claim 1 , further comprising tetramethylammonium silicate and (3-aminopropyl) silane triol.
9. The composition of claim 1 , further comprising tetramethylammonium silicate or tetraortho silicate.
10. A composition comprising: concentrated phosphoric acid, in an amount of at least 60 weight percent, based on the total weight of the composition; a compound chosen from linear and branched C 8 -C 16 alkylbenzenesulfonic acids and C 6 -C 12 alkyldiphenyl oxide disulfonic acids; and a compound of the formula
wherein each R is independently chosen from C 1 -C 4 alkyl.
11. The composition of claim 10 , wherein each R is methyl.
12. The composition of claim 10 , wherein the compound chosen from chosen from linear and branched C 8 -C 16 alkylbenzenesulfonic acids and C 6 -C 12 alkyldiphenyl oxide disulfonic acids is chosen from
hexyl diphenyl oxide disulfonic acid;
tetrapropyl-(sulfophenoxy)-benzenesulfonic acid;
dodecylbenzenesulfonic acid; and
4-octylbenzenesulfonic acid.
13. The composition of claim 10 , further comprising a compound chosen from
N-(3-trimethoxysilylpropyl)diethylenetriamine;
N-(2-aminoethyl)-3-aminopropyltriethoxy silane;
N-(2-aminoethyl)-3-aminopropyl silane triol;
N 1 -(3-trimethoxysilylpropyl)diethylenetriamine;
N-(6-aminohexyl)aminopropyltrimethoxysilane;
(3-aminopropyl)triethoxy-silane; and
(3-aminopropyl)silane triol.
14. The composition of claim 10 , further comprising tetramethylammonium silicate and (3-aminopropyl) silane triol.