Metal etchant compositions and methods of fabricating a semiconductor device using the same

1. A method of fabricating a semiconductor device, the method comprising:

providing a substrate having a metal-containing layer formed thereon; and

etching the metal-containing layer using a metal etchant composition,

wherein etching the metal-containing layer is carried out in a process chamber comprising two separate inlets,

wherein etching the metal-containing layer comprises:

providing a composition consisting of a supercritical fluid;

mixing the metal etchant composition and a first portion of the composition consisting of the supercritical fluid in a storage unit to prepare a mixture; and

providing the mixture of the metal etchant composition and the first portion of the composition consisting of the supercritical fluid stored in the storage unit through a first inlet of the two separate inlets and providing a second portion of the composition consisting of the supercritical fluid through a second inlet of the two separate inlets onto the metal-containing layer at the same time, and

wherein the metal etchant composition comprises:

an organic peroxide in a concentration in a range of about 0.1 to about 20 wt. % based on a total weight of the metal etchant composition;

an organic acid in a concentration in a range of about 0.1to about 70 wt. % based on the total weight of the metal etchant composition; and

an alcohol-based solvent in a concentration in a range of about 10 to about 99.8 wt. % based on the total weight of the metal etchant composition.

2. The method of claim 1 , wherein the organic peroxide includes at least one peroxy ester having a structure of Formula 1, at least one peroxy acid having a structure of Formula 2, at least one diacyl peroxide having a structure of Formula 3, and/or at least one peroxy dicarbonate having a structure of Formula 4,

wherein R and R′ are each independently a hydrocarbon compound.

3. The method of claim 2 , wherein the organic peroxide includes at least one of t-butyl peroxyacetic acid, lauroyl peroxide, or ethyl peroxy dicarbonate.

4. The method of claim 1 , wherein the organic acid comprises carbon and 3 to 11 fluorine atoms or 3 to 35 hydrogen atoms.

5. The method of claim 4 , wherein the organic acid includes at least one of 2,2,2-trifluoroethanoic acid (CF 3 COOH), 2,2,3,3,4,4,4-heptafluorobutanoic acid (CF 3 CF 2 CF 2 COOH), acetic acid (CH 3 COOH), or butanoic acid (CH 3 CH 2 CH 2 COOH).

6. The method of claim 1 , wherein the alcohol-based solvent includes 1 to 15 carbon atom(s).

7. The method of claim 1 , wherein the supercritical fluid is a supercritical carbon dioxide fluid.

8. The method of claim 1 , wherein etching the metal-containing layer is performed at a temperature in a range of about 31° C. to about 100° C. and at a pressure in a range of about 73 bar to about 200 bar.

9. The method of claim 1 , wherein etching the metal-containing layer is performed in an anhydrous system.

10. A method of fabricating a semiconductor device, the method comprising:

providing a substrate having a metal-containing layer formed thereon; and

removing the metal-containing layer using a metal etchant composition,

wherein removing the metal-containing layer is carried out in a process chamber comprising two separate inlets,

wherein removing the metal-containing layer comprises:

providing a composition consisting of a supercritical fluid;

mixing the metal etchant composition and a first portion of the composition consisting of the supercritical fluid in a storage unit to prepare a mixture; and

providing the mixture of the metal etchant composition and the first portion of the composition consisting of the supercritical fluid stored in the storage unit through a first inlet of the two separate inlets and providing a second portion of the composition consisting of the supercritical fluid through a second inlet of the two separate inlets onto the metal containing layer at the same time, and

wherein the metal etchant composition comprises:

an organic peroxide;

an organic acid; and

an alcohol-based solvent,

wherein the metal etchant composition is anhydrous.

11. The method of claim 10 , wherein the organic peroxide and the organic acid are present in the metal etchant composition in a ratio in a range of about 1:1 to about 1:5(organic peroxide:organic acid).

12. The method of claim 10 , wherein the metal etchant composition provides an etch rate of the metal-containing layer of about 15 Å/hour to about 40Å/hour.

13. The method of claim 10 , wherein the organic peroxide is present in a concentration in a range of about 0.1 to about 20 wt. % based on a total weight of the metal etchant composition,

wherein the organic acid is present in a concentration in a range of about 0.1 to about 70wt. % based on the total weight of the metal etchant composition, and

wherein the alcohol-based solvent is present in a concentration in a range of about 10 to about 99.8 wt. % based on the total weight of the metal etchant composition.

14. The method of claim 10 , wherein the metal-containing layer is a titanium (Ti) layer, a tantalum (Ta) layer, an aluminum (Al) layer, a tungsten (W) layer, or a copper (Cu) layer.

15. A method of fabricating a semiconductor device, the method comprising:

providing a substrate having a metal-containing layer formed thereon; and

removing the metal-containing layer using a metal etchant composition,

wherein removing the metal-containing layer comprises:

providing a composition consisting of a supercritical fluid;

mixing the metal etchant composition and a first portion of the composition consisting of the supercritical fluid in a storage unit to prepare a mixture; and

providing the mixture of the metal etchant composition and the first portion of the composition consisting of the supercritical fluid stored in the storage unit, through a first inlet of two separate inlets of a process chamber, on the metal-containing layer, and providing a second portion of the composition consisting of the supercritical fluid, through a second inlet of the two separate inlets of the process chamber, on the metal-containing layer,

wherein providing the mixture and providing the second portion of the composition consisting of the supercritical fluid are performed at the same time,

wherein the metal etchant composition comprises:

an organic peroxide in a concentration in a range of about 0.1 to about 20 wt. % based on a total weight of the metal etchant composition;

an organic acid in a concentration in a range of about 0.1 to about 70 wt. % based on the total weight of the metal etchant composition; and

an alcohol-based solvent selected from the group consisting of methanol, ethanol, propanol, isopropanol, heptanol, octanol and any combination thereof, and

wherein the metal-containing layer is a titanium (Ti) layer, a titanium nitride (TiN) layer, a tantalum (Ta) layer, a tantalum nitride (TaN) layer, an aluminum (Al) layer, a tungsten (W) layer, or a copper (Cu) layer.

16. The method of claim 1 , wherein the metal-containing layer comprises a titanium nitride layer, and

wherein the alcohol-based solvent is selected from the group consisting of ethanol, isopropanol and a combination thereof.

17. The method of claim 15 , wherein the supercritical fluid is a supercritical carbon dioxide fluid, and

wherein removing the metal-containing layer is performed at a temperature in a range of about 31° C. to about 100° C. and at a pressure in a range of about 73 bar to about 200 bar.