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US 10,472,567 B2Granted
Compositions and methods for selectively etching titanium nitride
AssigneeEntegris, Inc.
InventorsLi-Min Chen, Emanuel I. Cooper, Steven Lippy, Lingyan Song, Chia-Jung Hsu, Sheng-Hung Tu, Chieh Ju Wang
Life of this patent
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Abstract
Semi-aqueous compositions useful for the selective removal of titanium nitride and/or photoresist etch residue materials relative to metal conducting, e.g., tungsten and copper, and insulating materials from a microelectronic device having same thereon. The semi-aqueous compositions contain at least one oxidant, at least one etchant, and at least one organic solvent, may contain various corrosion inhibitors to ensure selectivity.
Claims14
A semi-aqueous composition comprising:
- at least one oxidizing agent, wherein the oxidizing agent is present in amount ranging from 0.001 wt % to 0.2 wt % and comprises a species selected from the group consisting of periodic acid, iodic acid, vanadium (V) oxide, vanadium (IV,V) oxide, ammonium vanadate 1,4-benzoquinone, dimethyl-1,4-benzoquinone, and combinations thereof,
- from 0.1 wt % to 2.5 wt % of at least one etchant,
- from 0.001 wt % to about 2 wt % of at least one corrosion inhibitor selected from the group consisting of myristyltrimethylammonium bromide, benzalkonium chloride, hexadecyltrimethylammonium p-toluenesulfonate, hexadecyltrimethylammonium hydroxide, 5-benzyl-1H-tetrazole, and combinations thereof,
- from 0.01 wt % to 2 wt % of at least one source of silica selected from the group consisting of methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane (TEOS), N-propyltrimethoxysilane, N-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, ammonium hexafluororosilicate, sodium silicate, tetramethyl ammonium silicate (TMAS), and combinations thereof,
- from 85 wt % to 99 wt % water, and
- from 1 wt % to 15 wt % of at least one organic solvent;
- said composition substantially devoid of amines, chemical mechanical polishing abrasive materials, and hydrogen peroxide, the composition characterized by a TiN to tungsten selectivity of greater than 40:1 and a tungsten removal rate less than about 1 Å min−1 when tungsten and TiN coupons are immersed in said composition at 50° C.
4 more elements
A semi-aqueous composition for selectively removing titanium nitride and/or photoresist etch residue material from the surface of a microelectronic device having same thereon, said composition comprising:
- at least one oxidizing agent present in amount ranging from 0.001 wt % to 0.2 wt % and selected from the group consisting of periodic acid, iodic acid, vanadium (V) oxide, vanadium (IV,V) oxide, ammonium vanadate, 1,4-benzoquinone, dimethyl-1,4-benzoquinone, and combinations thereof,
- from 0.1 wt % to 2.5 wt % of at least one etchant,
- from 0.001 wt % to 2 wt % of at least one corrosion inhibitor selected from the group consisting of myristyltrimethylammonium bromide, benzalkonium chloride, hexadecyltrimethylammonium p-toluenesulfonate, hexadecyltrimethylammonium hydroxide, 5-benzyl-1H-tetrazole, and combinations thereof,
- from 0.01 wt % to 2 wt % of at least one source of silica selected from the group consisting of methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane (TEOS), N-propyltrimethoxysilane, N-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, ammonium hexafluororosilicate, sodium silicate, tetramethyl ammonium silicate (TMAS), and combinations thereof,
- from 85 wt % to 95 wt % water, and
- from 1 wt % to 15 wt % of at least one organic solvent;
- wherein the composition is substantially devoid of hydrogen peroxide.
4 more elements
A method comprising contacting a surface of a microelectronic device comprising titanium nitride material, copper, tungsten, and low-k dielectric materials with a semi-aqueous composition, comprising:
- at least one oxidizing agent present in amount ranging from 0.001 wt % to 0.2 wt % and selected from the group consisting of periodic acid, iodic acid, vanadium (V) oxide, vanadium (IV,V) oxide, ammonium vanadate, 1,4-benzoquinone, dimethyl-1,4-benzoquinone, and combinations thereof;
- from 0.1 wt % to 2.5 wt % of at least one etchant;
- from 0.001 wt % to 2 wt % of at least one corrosion inhibitor selected from the group consisting of myristyltrimethylammonium bromide, benzalkonium chloride, hexadecyltrimethylammonium p-toluenesulfonate, hexadecyltrimethylammonium hydroxide, 5-benzyl-1H-tetrazole, and combinations thereof,
- from 0.01 wt % to 2 wt % of at least one source of silica selected from the group consisting of methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane (TEOS), N-propyltrimethoxysilane, N-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, ammonium hexafluororosilicate, sodium silicate, tetramethyl ammonium silicate (TMAS), and combinations thereof,
- from 85 wt % to 95 wt % water, and
- from 1 wt % to 15 wt % of at least one organic solvent;
- said composition substantially devoid of amines, chemical mechanical polishing abrasive materials, and hydrogen peroxide, the composition characterized by a TiN to tungsten selectivity of greater than 40:1 and a tungsten removal rate less than about 1 Å min−1 when tungsten and TiN coupons are immersed in said composition at 50° C.
4 more elements
Dependencies are inferred from the claim text.