Copper corrosion inhibition system

Patent metadata

Field	Value
Publication number	US-9957469-B2
Application number	US-201514790966-A
Country	US
Kind code	B2
Filing date	Jul 2, 2015
Priority date	Jul 14, 2014
Publication date	May 1, 2018
Grant date	May 1, 2018

Abstract

There are provided metal corrosion inhibition cleaning compositions, methods and system for copper (Cu), tungsten (W), titanium (Ti), tantalum (Ta), cobalt (Co), and aluminum (Al). The metal corrosion inhibition cleaning compositions provide corrosion inhibition effects by use a combination of two chemicals—at least one multi-functional amine that has more than one amino groups; and at least one multi-functional acid that has more than one carboxylate groups. The metal corrosion inhibition cleaning compositions are effective for cleaning the residues deriving from high density plasma etching followed by ashing with oxygen containing plasmas; and slurry particles and residues remaining after chemical mechanical polishing (CMP).

First claim

The invention claimed is:

1. A metal corrosion inhibition cleaning composition consisting of:
1) 0.1 wt. % to 5 wt. % of at least one multi-functional acid;
2) 0.1 wt. % to 25 wt. % of at least one multi-functional amine;
3) fluoride source;
4) up to 70 wt. % liquid carrier; and
5) base;
wherein
the multi-functional amine is an amine or a polyamine that has more than one amino groups in one molecule;
the multi-functional acid is an acid or a multi-acid that has more than one carboxylate groups in one molecule selected from the group consisting of malic acid, phthalic acid; citric acid, trimellitic acid, pyromellitic acid, and combinations thereof; and
the liquid carrier is selected from the group consisting of organic solvent, water, and combinations thereof.

2. The metal corrosion inhibition cleaning composition of claim 1 , wherein the multi-functional amine is selected from the group consisting of polyethylenimine, triamine, pentamine, hexamine, and combinations thereof.

3. The metal corrosion inhibition cleaning composition of claim 1 , wherein the organic solvent is selected from the group consisting of propylene glycol (PG), glycol ethers, aprotic solvents such as N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAC), sulfolane, dimethylformamide (DMF) and combinations thereof.

4. The metal corrosion inhibition cleaning composition of claim 1 , wherein the fluoride source is selected from the group consisting of hydrofluoric acid (HF), ammonium fluoride (NH 4 F), ammonium bifluoride (NH 4 HF 2 ), tetramethylammonium fluoride (TMAF), and combinations thereof; and the fluoride source ranges from 0.01 wt % to 5.67 wt %; the base is selected from the group consisting of triethanolamine (TEA) and substituted derivatives, diethanolamine and substituted derivatives, monoethanolamine and substituted derivatives, and combinations thereof; and the base ranges up to 50 wt. %.

5. The metal corrosion inhibition cleaning composition of claim 4 , wherein the multi-functional amine is selected from the group consisting of polyethylenimine, triamine, pentamine, hexamine, and combinations thereof; and the multi-functional acid is selected from the group consisting of malic acid, citric acid; and combinations thereof.

6. The metal corrosion inhibition cleaning composition of claim 1 , wherein pH of the metal corrosion inhibition cleaning composition ranges from 5 to 10; and at least one of the multi-functional acid and the multi-functional amine is non-polymeric.

7. A method of cleaning a semiconductor wafer comprising:
a) providing the semiconductor wafer having at least a surface containing at least one metal and residues;
b) providing a metal corrosion inhibition cleaning composition consisting of;
1) 0.1 wt. % to 5 wt. % of at least one multi-functional acid;
2) 0.1 wt. % to 25 wt. % of at least one multi-functional amine;
3) up to 70 wt. % liquid carrier;
4) fluoride source; and
5) base;
wherein
the multi-functional amine is an amine or a polyamine that has more than one amino groups in one molecule;
the multi-functional acid is an acid or a multi-acid that has more than one carboxylate groups in one molecule selected from the group consisting of malic acid, phthalic acid; citric acid, trimellitic acid, pyromellitic acid, and combinations thereof; and
the liquid carrier is selected from the group consisting of organic solvent, water, and combinations thereof;

c) contacting the semiconductor wafer with the metal corrosion inhibition cleaning composition; and
d) cleaning the residues;
wherein at least a portion of the surface having the residues is in contact with the metal corrosion inhibition composition.

8. The method of cleaning a semiconductor wafer of claim 7 , wherein the metal is selected from the group consisting of copper (Cu), tungsten (W), titanium (Ti), tantalum (Ta), cobalt (Co), and aluminum (Al) and combinations thereof; the residues are from high density plasma etching followed by ashing with oxygen containing plasmas; and from chemical mechanical polishing (CMP).

9. The method of cleaning a semiconductor wafer of claim 7 , wherein the metal is copper (Cu).

10. The method of cleaning a semiconductor wafer of claim 7 , wherein
the multi-functional amine is selected from the group consisting of polyethylenimine, triamine, pentamine, hexamine, and combinations thereof;
and
the organic solvent is selected from the group consisting of propylene glycol (PG), glycol ethers, aprotic solvents such as N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAC), sulfolane, dimethylformamide (DMF) and combinations thereof.

11. The method of cleaning a semiconductor wafer of claim 7 , wherein pH of the metal corrosion inhibition cleaning composition ranges from 5 to 10; and at least one of the multi-functional acid and the multi-functional amine is non-polymeric.

12. The metal corrosion inhibition cleaning composition of claim 7 , wherein the fluoride source is selected from the group consisting of hydrofluoric acid (HF), ammonium fluoride (NH 4 F), ammonium bifluoride (NH 4 HF 2 ), tetramethylammonium fluoride (TMAF), and combinations thereof; and the fluoride source ranges from 0.01 wt % to 5.67 wt %; the base is selected from the group consisting of triethanolamine (TEA) and substituted derivatives, diethanolamine and substituted derivatives, monoethanolamine and substituted derivatives, and combinations thereof; and the base ranges up to 50 wt. %.

13. A semiconductor wafer cleaning system comprising:
a semiconductor wafer having at least a surface containing at least one metal and residues;
a metal corrosion inhibition cleaning composition consisting of:
1) 0.1 wt. % to 5 wt. % of at least one multi-functional acid;
2) 0.1 wt. % to 25 wt. % of at least one multi-functional amine;
3) fluoride source;
4) up to 70 wt. % liquid carrier; and
5) base;
wherein
the multi-functional amine is an amine or a polyamine that has more than one amino groups in one molecule;
the multi-functional acid is an acid or a multi-acid that has more than one carboxylate groups in one molecule selected from the group consisting of malic acid, phthalic acid; citric acid, trimellitic acid, pyromellitic acid, and combinations thereof; and
the liquid carrier is selected from the group consisting of organic solvent, water, and combinations thereof;

wherein
at least a portion of the surface having the residues is in contact with the cleaning composition.

14. The semiconductor wafer cleaning system of claim 13 , wherein the metal is selected from the group consisting of copper (Cu), tungsten (W), titanium (Ti), tantalum (Ta), cobalt (Co), and aluminum (Al) and combinations thereof; the residues are from high density plasma etching followed by ashing with oxygen containing plasmas; and from chemical mechanical polishing (CMP).

15. The semiconductor wafer cleaning system of claim 13 , wherein the fluoride source is selected from the group consisting of hydrofluoric acid (HF), ammonium fluoride (NH 4 F), ammonium bifluoride (NH 4 HF 2 ), tetramethylammonium fluoride (TMAF), and combinations thereof; and the fluoride source ranges from 0.01 wt % to 5.67 wt %; and the base is selected from the group consisting of triethanolamine (TEA) and substituted derivatives, diethanolamine and substituted derivatives, monoethanolamine and substituted derivatives, and combinations thereof; and the base ranges up to 50 wt %.

16. The semiconductor wafer cleaning system of claim 15 , wherein the multi-functional amine is selected from the group consisting

Assignees

• Versum Mat Us Llc

Inventors

• Liu Wen Dar
• Inaoka Seiji
• Lee Yi-Chia
• Derecskei-Kovacs Agnes

Classifications

• H10P72/0411

  for wet cleaning or washing · CPC title

• H10P70/27

  during, before or after processing of conductive materials, e.g. polysilicon or amorphous silicon layers · CPC title

• H10P70/277 Primary

  the processing being a planarisation of conductive layers · CPC title

• C11D7/3209

  Amines or imines with one to four nitrogen atoms; Quaternized amines · CPC title

• H01L21/02068

  Electricity · mapped topic