Wet etching composition and method
The invention provides a composition and method for improving the selectivity of nitride etching versus oxide etching and can be used with conventional phosphoric acid wet etch compositions. The invention describes additives that serve to inhibit silicon, oxides, and related compounds regrowth (i.e., redeposition) on the silicon oxide surface. In certain embodiments, the invention provides certain amino-substituted aryl compounds which are bound to a tri-alkoxy silane.
1. A selective etching composition comprising the reaction product of:
(a) (i) a compound of Formula(I)
wherein A is an aromatic ring or a heteroaromatic ring, and wherein each R 1 is the same or different and is chosen from hydrogen, hydroxyl, C 1 -C 20 alkyl, C 1 -C 20 alkylamino, phenyl, benzyl, and C 1 -C 20 alkoxy, phenoxy, and C 3 -C 8 cycloalkyl; x is 0 or 1; each y and y′ may be the same or different and is zero or is chosen from an integer of from 1 to 5; z is an integer chosen from 1, 2, or 3; m is an integer chosen from 1, 2, or 3; w is zero or an integer chosen from 1, 2, 3, or 4 and m+z=4; or
(ii) a compound of Formula (II)
(R 1 ) 3 Si-M-Si(R 1 ) 3 (II)
wherein each R 1 is the same or different and is as defined above, and -M- is chosen from —NH— or —O—;
(b) phosphoric acid, comprising at least 50 wt. % of the selective etching composition;
(c) a solvent comprising water; and
(d) a primary, secondary, or tertiary amine, C 1 -C 6 alkanolamine, or dihydrogen phosphate salt thereof, or a nitrogen-containing heterocyclic ring, optionally substituted by with one to three groups chosen from C 1 -C 20 alkyl, C 1 -C 20 alkoxy, —CN, —NO 2 , C 1 -C 20 alkoxycarbonyl, C 1 -C 20 alkanoyloxy, C 1 -C 20 alkylsulfonyl, hydroxyl, carboxyl, halo, phenyl, benzyl, amino-C 1 -C 20 alkyl, ——C 1 -C 20 alkyl-SO 3 H, ——C 1 -C 20 alkyl-PO 3 H 2 , and groups of the formula —N(R 1 ) 2 .
2. The selective etching composition of claim 1 , wherein the primary, secondary, or tertiary amine is chosen from trimethylamine, triethylamine, tripropylamine, tributylamine, N,N-dimethylaniline, or N-methylaniline.
3. The selective etching composition of claim 1 , wherein the compound of Formula (I) has the following structure:
wherein R 1 is as defined in claim 1 , and each R 2 is the same or different and is chosen from H and C 1 -C 20 alkyl.
4. The selective etching composition of claim 1 , wherein component (a) is triphenylsilanol.
5. The selective etching composition of claim 1 , wherein component (a) is p-aminophenyl trimethoxysilane.
6. The selective etching composition of claim 1 , wherein each R 1 is the same or different and is chosen from hydroxyl, C 1 -C 20 alkoxy, and C 1 -C 20 alkylamino, and y, y′, and x are zero.
7. The selective etching composition of claim 1 , wherein component (a) is a compound of Formula (I), further comprising a compound of Formula (II), wherein R 1 is C 1 -C 20 alkyl.
8. The selective etching composition of claim 1 further comprising 3-aminopropylsilane triol and/or tetramethylammonium silicate.
9. The selective etching composition of claim 1 , wherein the compound of Formula (I) is chosen from p-aminophenyl trimethoxysilane, triphenyl silanol, and 2-(4-pyridylethyl)triethoxysilane.
10. The selective etching composition of claim 1 , wherein the compound of Formula (II) is hexamethyldisiloxane.
11. The selective etching composition of claim 1 , further comprising one or more water-miscible solvents which is selected from pyrrolidinones, glycols, amines, and glycol ethers.
12. The selective etching composition of claim 1 , further comprising one or more surfactants.
13. The selective etching composition of claim 1 , further comprising one or more polymers.
14. A selective etching composition comprising the reaction product of:
(a) (i) a compound of Formula(I)
wherein A is an aromatic ring or a heteroaromatic ring, and wherein each R 1 is the same or different and is chosen from hydrogen, hydroxyl, C 1 -C 20 alkyl, C 1 -C 20 alkylamino, phenyl, benzyl, and C 1 -C 20 alkoxy, phenoxy, and C 3 -C 8 cycloalkyl; x is 0 or 1; each y and y′ may be the same or different and is zero or is chosen from an integer of from 1 to 5; z is an integer chosen from 1, 2, or 3; m is an integer chosen from 1, 2, or 3; w is zero or an integer chosen from 1, 2, 3, or 4 and m+z=4; or
(ii) a compound of Formula (II)
(R 1 ) 3 Si-M-Si(R 1 ) 3 (II)
wherein each R 1 is the same or different and is as defined above, and -M- is chosen from —NH— or —O—;
(b) phosphoric acid, comprising at least 50 wt. % of the selective etching composition;
(c) a solvent comprising water; and
(d) a fluoride compound chosen from HF; monofluorphosphoric acid; fluorosilicic acid; fluoroboric acid; tetramethylammonium hexafluorophosphate; ammonium fluoride; ammonium bifluoride; quaternary ammonium tetrafluoroborates and quaternary phosphonium tetrafluoroborates having the formula NR′ 4 BF 4 and PR′ 4 BF 4 , respectively, wherein R′ may be the same as or different from one another and is selected from hydrogen, straight-chained, branched, or cyclic C 1 -C 6 alkyl, and straight-chained or branched C 6 -C 10 aryl; tetrabutylammonium tetrafluoroborate (TBA-BF 4 ); cesium fluoride; potassium fluoride; and combinations thereof.