Etching composition, a method of etching a metal barrier layer and a metal layer using the same, and method of manufacturing semiconductor device using the same

A method of etching a titanium nitride layer and a tungsten layer, the method comprising:

• forming the titanium nitride layer and the tungsten layer on a substrate;
• and
• using an etching composition to etch the titanium nitride layer and the tungsten layer,
• wherein the etching composition includes:
• an oxidant selected from the group consisting of nitric acid, bromic acid, iodic acid, perchloric acid, perbromic acid, periodic acid, sulfuric acid, methane sulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, and a combination thereof;
• a metal etching inhibitor including an amine-based compound having one or two amino groups;
• and
• a metal oxide solubilizer selected from the group consisting of phosphoric acid, phosphate, carboxylic acid having 3 to 20 carbon atoms, and a combination thereof,
• wherein the etching composition is selected to obtain an etch selectivity of from 1.0 to 2.0, where the etch selectivity is a ratio of an etch rate of the tungsten layer to an etch rate of the titanium nitride layer, and
• the metal etching inhibitor is selected to reduce the etch rate of the tungsten layer to thereby reduce the etch selectivity as compared to a corresponding etching composition being the same as the etching composition except for not containing the metal etching inhibitor.

A method of manufacturing a semiconductor device, the method comprising:

• forming sacrificial layers and dielectric layers that are alternately and repeatedly stacked on a substrate;
• selectively removing the sacrificial layers to form recess regions;
• forming a metal barrier layer and a metal layer that fill the recess regions;
• and
• using an etching composition to partially etch the metal barrier layer and the metal layer to form a metal barrier pattern and a metal pattern in each of the recess regions,
• wherein the etching composition includes:
• an oxidant selected from the group consisting of nitric acid, bromic acid, iodic acid, perchloric acid, perbromic acid, periodic acid, sulfuric acid, methane sulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, and a combination thereof;
• a metal etching inhibitor including an amine-based compound having one or two amino groups;
• and
• a metal oxide solubilizer selected from the group consisting of phosphoric acid, phosphate, carboxylic acid having 3 to 20 carbon atoms, and a combination thereof,
• wherein the etching composition is selected to obtain an etch selectivity of from 1.0 to 2.0, where the etch selectivity is a ratio of an etch rate of the metal layer to an etch rate of the metal barrier layer,
• the metal etching inhibitor is selected to reduce the etch rate of the metal layer to thereby reduce the etch selectivity as compared to a corresponding etching composition being the same as the etching composition except for not containing the metal etching inhibitor,
• the metal layer includes at least one of tungsten, aluminum, copper, molybdenum, or cobalt, and
• the metal barrier layer includes at least one of a titanium nitride (TiN) layer, a tantalum nitride (TaN) layer, a tungsten nitride (WN) layer, a nickel nitride (NiN) layer, a cobalt nitride (CoN) layer, or a platinum nitride (PtN) layer.