Method of and system for cleaning a semiconductor wafer simultaneously using electrolytically ionized water and diluted hydrofluoric acid

• US 20030062068A1
• Filed: 05/01/2002
• Published: 04/03/2003
• Est. Priority Date: 07/10/2001
• Status: Abandoned Application

• Current Assignee: Samsung Electronics Co. Ltd.
• Original Assignee: Samsung Electronics Co. Ltd.
• Inventors: Ha, Song-Rok, Lee, Kun-Tack, Ko, Hyung-Ho, Park, Im-Soo, Han, Yong-Pil
• Application Number:
  US10/135,452
• Publication Number:
  US 20030062068A1
• Time in Patent Office: Days
• US Class Current: 134/28
• CPC Class Codes: B08B 3/08 the liquid having chemical or dissolving effect substances used, see the relevant classes
• CPC Class Codes: C02F 1/4618 for producing "ionised" acidic or basic water
• CPC Class Codes: C02F 2001/46161 Porous electrodes
• CPC Class Codes: C02F 2001/46195 characterised by the oxidation reduction potential [ORP]
• CPC Class Codes: C02F 2103/04 for obtaining ultra-pure water
• CPC Class Codes: C02F 2201/46115 Electrolytic cell with membranes or diaphragms
• CPC Class Codes: C02F 2201/4617 DC only
• CPC Class Codes: C02F 2209/04 Oxidation reduction potential [ORP]
• CPC Class Codes: C02F 2209/06 pH
• CPC Class Codes: C11D 11/0047 Electronic devices, e.g. PCBs or semiconductors
• CPC Class Codes: C11D 2111/22 Electronic devices, e.g. PCBs or semiconductors
• CPC Class Codes: C11D 7/08 Acids
• CPC Class Codes: H01L 21/02074 the processing being a planarization of conductive layers

Abstract

The surface of a semiconductor wafer is cleaned simultaneously using diluted hydrofluoric acid and electrolytic ionized water. The electrolytic ionized water is produced using an electrolyte supplied into an intermediate cell of a 3-cell electrolyzer. The 3-cell electrolyzer has an anode cell, the intermediate cell, and a cathode cell partitioned from one another by ion exchange membranes. After deionized water is supplied into the anode cell and the cathode cell and the intermediate cell is filled with an electrolytic aqueous solution, electrolysis is carried out to produce electrolytic ionized water. The electrolytic ionized water and the hydrofluoric acid solution are then supplied to one or more semiconductor wafer cleaning apparatus. The simultaneous use of the electrolytic ionized water and the diluted hydrofluoric acid offers an improvement in removing contaminants from the surface of the wafer without damaging an insulating layer or a metal layer exposed at the surface of the semiconductor wafer.

Claims

1. A method of cleaning a semiconductor wafer, comprising steps of:

providing an electrolyzer that includes an anode, a cathode, an intermediate cell located between the anode and the cathode, at least one ionizing cell disposed adjacent the intermediate cell and containing a respective one of said anode and said cathode, and a respective ion exchange membrane partitioning each said at least one ionizing cell from the intermediate cell;

supplying deionized water into the at least one ionizing cell of the electrolyzer;

performing electrolysis of an electrolytic aqueous solution in the intermediate cell while the deionized water is in said at least one ionizing cell, to produce electrolytically ionized water in the at least one ionizing cell; and

supplying the ionized water and a sloution of diluted hydrofluoric acid (HF) at the same time onto the surface of the semiconductor wafer.

2. The cleaning method of claim 1, wherein the ionized water and hydrofluoric acid (HF) solution are supplied at the same time onto the surface of a semiconductor wafer having an exposed low-k dielectric layer whose dielectric constant is smaller than that of silicon dioxide.

3. The cleaning method of claim 2, wherein the dielectric layer is formed of a material selected from the group consisting of hydrogen silsequioxane, fluorosilicate glass, polyimide, benzocyclobutene (BCB), Silk (Silicon insulator Low-k), hybrid organic siloxane polymer, and xerogel.

4. The cleaning method of claim 1, wherein the hydrofluoric acid solution contains 0.06-0.7% by weight hydrofluoric acid.

5. The cleaning method of claim 1, wherein the ionized water and the hydrofluoric acid solution are simultaneously supplied onto the surface of the semiconductor wafer during an initial stage of cleaning, and further comprising subsequently supplying only the ionized water onto the surface of the semiconductor wafer during a final stage of cleaning.

6. The cleaning method of claim 1, wherein the at least one ionizing cell comprises an anode cell containing the anode and a cathode cell containing the cathode, and said electrolysis produces anode water, containing oxidative substances, in the anode cell and cathode water, containing reductive substances, in the cathode cell.

7. The cleaning method of claim 6, wherein the anode water and the hydrofluoric acid solution are simultaneously supplied onto the surface of the semiconductor wafer during an initial stage of cleaning, and further comprising subsequently supplying the anode water and the cathode water sequentially onto the surface of the semiconductor wafer during a final stage of cleaning.

8. The cleaning method of claim 7, wherein the anode water and the cathode water are sequentially supplied several times onto the surface of the semiconductor wafer during the final stage of cleaning.

9. The cleaning method of claim 1, wherein the electrolytic aqueous solution is an aqueous solution of 1-15% by weight ammonium hydroxide and 1-15% by weight fluoride.

10. The cleaning method of claim 9, wherein the fluoride is one of hydrogen fluoride and ammonium fluoride.

11. The cleaning method of claim 9, wherein the ionized water contains oxidative substances and has a pH of 2˜

6 and an oxidation-reduction potential (ORP) of +300˜

+1000 mV.

12. The cleaning method of claim 1, wherein the electrolytic aqueous solution is an aqueous solution of 3-15% by weight ammonium hydroxide.

13. The cleaning method of claim 12, wherein the ionized water contains oxidative substances and has a pH of 7˜

9 and an oxidation-reduction potential (ORP) of +100˜

+1000 mV.

14. The cleaning method of claim 1, wherein the electrolytic aqueous solution is an aqueous solution of 3-5% by weight hydrochloric acid.

15. The cleaning method of claim 14, wherein the ionized water contains oxidative substances and has a pH of 2˜

4 and an oxidation-reduction potential (ORP) of +700˜

+1000 mV.

16. A method of processing a semiconductor wafer in the manufacturing of a semiconductor device, comprising steps of :

performing a chemical mechanical polishing process on a semiconductor wafer having a metal layer on a low-k dielectric layer, whose dielectric constant is smaller than that of silicon dioxide, wherein the dielectric layer is exposed and impurities as the result of the process are produced on the surface of the semiconductor wafer; and

subsequently cleaning the surface of the semiconductor wafer, to remove the impurities produced by the chemical mechanical polishing process, by simultaneously supplying electrolytic ionized water and a solution of diluted hydrofluoric acid (HF) onto the polished surface of the wafer.

17. The processing method of claim 16, wherein the metal layer comprises copper.

18. The processing method of claim 16, wherein said cleaning of the surface of the semiconductor wafer comprises producing the ionized water by

providing an electrolyzer having a cathode, an anode, an intermediate cell located between the cathode and the anode, at least one ionizing cell adjacent the intermediate cell and containing a respective one of said anode and said cathode, and at least one ion exchange membrane partitioning said at least one ionizing cell from the intermediate cell,

supplying deionized water into the at least one ionizing cell of the electrolyzer, and

performing electrolysis of an electrolytic aqueous solution in the intermediate cell while the deionized water is in the at least one ionizing cell.

19. The processing method of claim 16, wherein said cleaning the surface of the semiconductor wafer comprises supplying the ionized water and the hydrofluoric acid solution simultaneously onto the surface of the semiconductor wafer during an initial stage of said cleaning, and subsequently supplying only the ionized water onto the surface of the semiconductor wafer during a final stage of said cleaning.

20. The processing method of claim 16, wherein the at least one ionizing cell comprises an anode cell in which the anode is disposed and a cathode cell in which the cathode is disposed, said supplying of deionized water comprises supplying deionized water into the anode cell and the cathode cell, and said electrolysis produces anode water, containing oxidative substances, in the anode cell and cathode water, containing reductive substances, in the cathode cell.

21. The processing method of claim 20, wherein said cleaning the surface of the semiconductor wafer comprises supplying the anode water and the hydrofluoric acid solution simultaneously onto the surface of the semiconductor wafer during an initial stage of said cleaning, and subsequently supplying the anode water and the cathode water sequentially onto the surface of the semiconductor wafer during a final stage of said cleaning.

22. The processing method of claim 21, wherein the anode water and the cathode water are sequentially supplied several times onto the surface of the semiconductor wafer during the final stage of cleaning.

23. The processing method of claim 20, wherein the electrolytic aqueous solution is an aqueous solution of 1-15% by weight ammonium hydroxide and 1-15% by weight fluoride.

24. The processing method of claim 20, wherein the electrolytic aqueous solution is an aqueous solution of 3-15% by weight ammonium hydroxide.

25. The processing method of claim 20, wherein the electrolytic aqueous solution is an aqueous solution of 3-5% by weight hydrochloric acid.

26. A cleaning system for use in cleaning the surface of a semiconductor wafer, said cleaning system comprising:

a 3-cell electrolyzer including an anode cell containing an anode, a cathode cell containing a cathode, an intermediate cell interposed between said anode cell and said cathode cell, and ion exchange membranes partitioning said intermediate cell from said anode cell and said cathode cell, respectively;

at least one semiconductor wafer cleaning apparatus for use in cleaning semiconductor wafers;

a source of a solution of diluted hydrofluoric acid, and at least one HF solution inlet line connecting said source of the solution of diluted hydrofluoric acid to said at least one semiconductor wafer cleaning apparatus; and

ionized water oulet lines connecting said anode cell and said cathode cell to said at least one semiconductor wafer cleaning apparatus, whereby the hydrofluoric acid solution and electrolytically ionized water from said 3-cell electrolyzer can be supplied to said at least one semiconductor wafer cleaning apparatus.

27. The cleaning system of claim 26, wherein said at least one semiconductor wafer cleaning apparatus comprises a pair of discrete semiconductor wafer cleaning apparatuses, and said ionized water oulet lines connect said anode cell and said cathode cell to said semiconductor wafer cleaning apparatuses, respectively.

28. The cleaning system of claim 26, wherein said ionized water outlet lines connect said anode cell and said cathode cell to the same said semiconductor wafer cleaning apparatus.

29. The cleaning system of claim 26, and further comprising a source of deionized water, and deionized water inlet lines connecting said source of deionized water to said anode cell and said cathode cell.

30. The cleaning system of claim 26, and further comprising a source of an aqueous electrolytic solution, an electrolytic solution inlet line connecting said source of an aqueous electrolytic solution to said intermediate cell, and a drain extending from said intermediate cell.

31. The cleaning system of claim 26, wherein the electrolytic aqueous solution is an aqueous solution of 1-15% by weight ammonium hydroxide and 1-15% by weight fluoride.

32. The cleaning system of claim 26, wherein the electrolytic aqueous solution is an aqueous solution of 3-15% by weight ammonium hydroxide.

33. The cleaning system of claim 26, wherein the electrolytic aqueous solution is an aqueous solution of 3-5% by weight hydrochloric acid.

34. The cleaning system of claim 26, wherein said ion exchange membranes comprise, between said anode cell and said intermediate cell, a fluorine-based cationic exchange membrane adjacent said anode cell and an anionic exchange membrane adjacent said intermediate cell.

35. The cleaning system of claim 26, wherein said ion exchange membranes comprise, between said cathode cell and said intermediate cell, an anionic exchange membrane adjacent said cathode cell and an cationic exchange membrane adjacent said intermediate cell.

36. The cleaning system of claim 26, wherein a DC power source is connected to said anode and cathode.