TiN hard mask and etch residue removal

1. A composition for selectively removing PVD titanium nitride (TiN or TiNxOy; where x=0 to 1.3 and y=0 to 2) from a semiconductor device comprising the PVD titanium nitride and a second material selected from the group consisting of Cu, Co, CVD titanium nitride, dielectric material, low-k dielectric material, and combinations thereof, the composition comprising:

1 to 20 wt % peroxide;

1-5 wt % base;

0.1-1 wt % carboxylic acid selected from the group consisting of citric acid, oxalic acid, malonic acid, lactic acid, adipic acid, acetic acid, iminodiacetic acid, and combinations thereof;

ammonium salt selected from the group consisting of ammonium citrate, ammonium acetate, ammonium malonate, ammonium adipate, ammonium lactate, ammonium iminodiacetate, ammonium chloride, ammonium bromide, ammonium fluoride, ammonium bifluoride, ammonium sulfate, and combinations thereof;

corrosion inhibitor, or 1-15 wt % of a long chain or mixed alkylammonium hydroxide, and combinations thereof, wherein said long chain or mixed alkylammonium hydroxide is selected from the group consisting of tetrabutylammonium hydroxide and mixed tetraalkylammonium hydroxide, wherein the alkylammonium cation contains alkyl groups of at least two different chain lengths; and

Solvent;

wherein the composition has a pH ranging from 7 to 11.5.

2. The composition of claim 1 , wherein the peroxide is selected from the group consisting of hydrogen peroxide, ammonium persulfate, peracidic acid, peroxybenzoic acid, and combinations thereof.

3. The composition of claim 1 , wherein the base is selected from the group consisting of tetraethylammonium hydroxide (TEAH), trimethylphenylammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, ammonium hydroxide, and combinations thereof.

4. The composition of claim 1 , wherein the composition comprises 25 to 5000 ppm of said corrosion inhibitor.

5. The composition of claim 1 , wherein the composition comprises 0.5-2 wt % of said ammonium salt.

6. The composition of claim 1 , wherein the corrosion inhibitor is selected from the group consisting of 1,2,4-triazole, benzotriazole, methyl-1H-benzotriazole, 2-aminobenthothiazole, benzimidazole, 2-mercapto-5-methylbenzimidaole, 8-hydroxyquinoline, 1-thioglycerol, ascorbic acid, pyrazole, and combinations thereof.

7. The composition of claim 1 , wherein the long chain or mixed alkyammonium hydroxide is selected from the group consisting of trimethylphenylammonium hydroxide(TMPAH), tetrabutylammonium hydroxide and mixed tetraalkylammonium hydroxide, wherein the alkylammonium cation contains alkyl groups of at least two different chain lengths.

8. The composition of claim 1 , wherein the solvent is selected from the group consisting of deionized water (DI water), purified water, distilled water, dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO 2 ), sulfolane ((CH 2 ) 4 SO 2 ), n-methylpyrrolidone, dipropyleneglycolmethylether, tripropyleneglycolmethyl ether, and combinations thereof.

9. The composition of claim 1 further comprises at least one selected from the group consisting of:

0.01 to 1 wt % of a chelating agent selected from the group consisting of glycine, iminodiacetic acid, nitrilotriacetic acid, glutamic acid, picolinic acid, ethylenediamine tetraacetic acid (EDTA), and combinations thereof;

100 ppm to 1000 ppm radical scavengers selected from the group consisting of manitol, polyalkylamines, (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl(TEMPO), diphenylamines, and combinations thereof; and

10 to 5000 ppm of long chain organic acids or amines.

10. The composition of claim 9 , wherein the long chain organic acid or amine is selected from the group consisting of decanonic acid, dodecanoic acid, dimer acid, hexylamine, surfactant salts of hexylamine, octylamine, surfactant salts of octylamine, dicyclohexylamine, surfactant salts of dicyclohexylamine, decylamine, surfactant salts of decylamine, dodecylamine, surfactant salt of dodecylamine, and combinations thereof.

11. The composition of claim 1 , wherein the composition comprises hydrogen peroxide, tetraethylammonium hydroxide, citric acid, ammonium citrate, methyl-1H-benzotriazole, and water.

12. The composition of claim 11 , wherein the composition further comprises tetraacetic acid (EDTA).

13. The composition of claim 1 , wherein the composition comprises hydrogen peroxide, tetraethylammonium hydroxide, citric acid, ammonium citrate, trimethylphenylammonium hydroxide (TMPAH), and water.

14. The composition of claim 13 , wherein the composition further comprises tetraacetic acid (EDTA).

15. The composition of claim 1 , wherein the composition comprises hydrogen peroxide, tetraethylammonium hydroxide, citric acid, ammonium citrate, benzotriazole, and water.

16. The composition of claim 15 , wherein the composition further comprises tetraacetic acid (EDTA).

17. The composition of claim 1 wherein the peroxide is present at from about 3 wt % to about 15 wt %.

18. The composition of claim 1 wherein the pH ranges from 8 to 10.5.

19. The composition of claim 1 wherein the composition exhibits a removal selectivity of PVD titanium nitride vs. the second material >2.

20. The composition of claim 1 wherein the peroxide is present from 1 to 9 wt %.

21. The composition of claim 1 wherein the peroxide is present at about 15 wt %.

22. A system for selectively removing PVD titanium nitride (TiN or TiNxOy, where x=0 to 1.3 and y=0 to 2) from a surface of a microelectronic device, comprising:

the semiconductor device comprising the PVD titanium nitride and a second material selected from Cu, Co, CVD titanium nitride dielectric material, low-k dielectric material and combinations thereof,

a composition comprising:

1 to 20 wt % peroxide;

1-5 wt % base;

0.1-1 wt % carboxylic acid selected from the group consisting of citric acid, oxalic acid, malonic acid, lactic acid, adipic acid, acetic acid, iminodiacetic acid, and combinations thereof;

ammonium salt selected from the group consisting of ammonium citrate, ammonium acetate, ammonium malonate, ammonium adipate, ammonium lactate, ammonium iminodiacetate, ammonium chloride, ammonium bromide, ammonium fluoride, ammonium bifluoride, ammonium sulfate, and combinations thereof;

corrosion inhibitor or 1-15 wt % of a long chain or mixed alkyammonium hydroxide, and combinations thereof;

Solvent;

and

optionally

0.01 to 1 wt % of a chelating agent selected from the group consisting of glycine, iminodiacetic acid, nitrilotriacetic acid, glutamic acid, picolinic acid, ethylenediamine tetraacetic acid (EDTA), and combinations thereof;

optionally 100 ppm to 1000 ppm radical scavengers selected from the group consisting of manitol, polyalkylamines, (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl(TEMPO), diphenylamines, and combinations thereof; and

optionally 10 to 5000 ppm of long chain organic acids or amines,

wherein the composition has a pH ranging from 7 to 11.5;

wherein the PVD titanium nitride and the second material are in direct contact with the composition.

23. A process of selectively removing PVD titanium nitride (TiN or TiNxOy, where x=0 to 1.3 and y=0 to 2) comprising:

providing a semiconductor device comprising the PVD titanium nitride and a second material selected from Cu, Co, CVD titanium nitride dielectric material, low-k dielectric material;

contacting the semiconductor device with a composition comprising:

1 to 20 wt % peroxide;

1-5 wt % base;

0.1-1 wt % carboxylic acid selected from the group consisting of citric acid, oxalic acid, malonic acid, lactic acid, adipic acid, acetic acid, iminodiacetic acid, and combinations thereof;

ammonium salt selected from the group consisting of ammonium citrate, ammonium acetate, ammonium malonate, ammonium adipate, ammonium lactate, ammonium iminodiacetate, ammonium chloride, ammonium bromide, ammonium fluoride, ammonium bifluoride, ammonium sulfate, and combinations thereof;

corrosion inhibitor or 1-15 wt % of a long chain or mixed alkyammonium hydroxide, and combinations thereof;

Solvent;

and

optionally

0.01 to 1 wt % of a chelating agent selected from the group consisting of glycine, iminodiacetic acid, nitrilotriacetic acid, glutamic acid, picolinic acid, ethylenediamine tetraacetic acid (EDTA), and combinations thereof;

optionally 100 ppm to 1000 ppm radical scavengers selected from the group consisting of manitol, polyalkylamines, (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl(TEMPO), diphenylamines, and combinations thereof; and

optionally 10 to 5000 ppm of long chain organic acids or amines,

wherein the composition has a pH ranging from 7 to 11.5;

selectively removing the PVD titanium nitride,

wherein the PVD titanium nitride and the second material are in direct contact with the composition, and the composition offers a removal selectivity of PVD titanium nitride vs. CVD titanium nitride >2, when the second material is CVD titanium nitride.

24. The process of claim 23 , wherein said composition comprises 25 to 5000 ppm of said corrosion inhibitor and 0.5-2 wt % of said ammonium salt.