Ruthenium containing layer deposition method

• US 7,438,949 B2
• Filed: 09/15/2005
• Issued: 10/21/2008
• Est. Priority Date: 01/27/2005
• Status: Active Grant

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Weidman, Timothy W.
• Primary Examiner(s): Meeks; Timothy
• Assistant Examiner(s): Burkhart; Elizabeth A
• Application Number:
  US11/228,649
• Publication Number:
  US 20060165892A1
• Time in Patent Office: 1,132 Days
• Field of Search: 427/248.1, 427/250
• US Class Current: 427/250
• CPC Class Codes: C23C 16/06 characterised by the deposition of metallic material
• CPC Class Codes: C23C 16/4488 by in situ generation of reactive gas by chemical or electrochemical reaction
• CPC Class Codes: C23C 16/45525 Atomic layer deposition [ALD]
• CPC Class Codes: C23C 16/45536 Use of plasma, radiation or electromagnetic fields
• CPC Class Codes: C23C 16/45544 characterized by the apparatus
• CPC Class Codes: C23C 16/5096 Flat-bed apparatus
• CPC Class Codes: H01L 21/28562 Selective deposition
• CPC Class Codes: H01L 21/76843 formed in openings in a dielectric
• CPC Class Codes: H01L 21/76873 for electroplating

Abstract

An exemplary apparatus and method of forming a ruthenium tetroxide containing gas to form a ruthenium containing layer on a surface of a substrate is described herein. The method and apparatus described herein may be especially useful for fabricating electronic devices that are formed on a surface of the substrate or wafer. Generally, the method includes exposing a surface of a substrate to a ruthenium tetroxide vapor to form a catalytic layer on the surface of a substrate and then filling the device structures by an electroless, electroplating, physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma enhanced CVD (PECVD), atomic layer deposition (ALD) or plasma enhanced ALD (PE-ALD) processes. In one embodiment, the ruthenium containing layer is formed on a surface of a substrate by creating ruthenium tetroxide in an external vessel and then delivering the generated ruthenium tetroxide gas to a surface of a temperature controlled substrate positioned in a processing chamber. In one embodiment, a ruthenium tetroxide containing solvent formation process is used to form ruthenium tetroxide using a ruthenium tetroxide containing source material. In one embodiment, of a ruthenium containing layer is formed on a surface of a substrate, using the ruthenium tetroxide containing solvent. In another embodiment, the solvent is separated from the ruthenium tetroxide containing solvent mixture and the remaining ruthenium tetroxide is used to form a ruthenium containing layer on the surface of a substrate.

Claims

1. A method of forming a ruthenium containing layer on a substrate surface, comprising:

forming a ruthenium tetroxide in a first vessel;

delivering an amount of the ruthenium tetroxide contained in the first vessel to a second vessel;

purging the second vessel to remove unwanted contaminants after the amount of the ruthenium tetroxide has been delivered to the second vessel from the first vessel; and

delivering an amount of ruthenium tetroxide contained in the second vessel to a substrate positioned on a substrate support in a vacuum processing chamber after purging the second vessel for a period of time, wherein the second vessel has a surface that is maintained at a temperature below about 25°

C. when the amount of ruthenium tetroxide is delivered.

2. A method of claim 1, wherein forming a ruthenium tetroxide in the first vessel comprises:

forming an ozone containing gas; and

delivering the ozone containing gas to a surface of a ruthenium containing material positioned in the first vessel.

3. A method of claim 2, wherein the ruthenium containing material is a material selected from the group consisting of sodium perruthenate and potassium perruthenate.

4. A method of claim 1, wherein delivering the amount of ruthenium tetroxide comprises flowing a first gas that comprises ruthenium tetroxide and oxygen or ozone to the second vessel, and purging the second vessel until the oxygen or ozone concentration is reduced to less than about 100 ppm.

5. A method of claim 1, wherein the substrate support is maintained at a temperature below about 350°

C.

6. A method of forming a ruthenium containing layer on a substrate surface, comprising:

forming a ruthenium tetroxide containing gas in a first vessel;

delivering an amount of the ruthenium tetroxide containing gas from the first vessel to a second vessel;

collecting a desired amount of ruthenium tetroxide from the ruthenium tetroxide containing gas on a surface of the second vessel that is maintained at a first temperature;

purging the second vessel to remove unwanted contaminants contained in the second vessel;

vaporizing an amount of the ruthenium tetroxide found on the surface of the second vessel; and

delivering an amount of the vaporized ruthenium tetroxide from the second vessel to a substrate positioned on a substrate support in a processing chamber to form a ruthenium containing layer on a surface of the substrate.

7. A method of claim 6, wherein the first temperature of the surface is between about −

20°

C. and about 25°

C.

8. A method of claim 6, wherein the vaporizing comprises:

heating the surface of the second vessel to a second temperature between about 0°

C. and about 25°

C.

9. A method of claim 6, wherein the processing chamber is a vacuum processing chamber that is adapted to process a substrate at a processing pressure between about 0.1 mTorr and about 50 Torr.

10. A method of forming a ruthenium containing layer on a substrate surface, comprising:

providing a solvent mixture that comprises a solvent and ruthenium tetroxide, wherein the solvent is selected from the group consisting of perfluorocarbons, hydroflurocarbons and chlorofluorocarbons; and

delivering the solvent mixture to a substrate positioned on a substrate support in a processing chamber.

11. A method of claim 10, wherein the solvent mixture is a perfluorocarbon, a hydroflurocarbon or a chlorofluorocarbon that is selected from the group consisting of perfluoropentane, perfluorohexane, fluorotrichloromethane and 1,1,2-trichloro-1,2,2-trifluoroethane.

12. A method of claim 10, wherein the substrate support is maintained at a temperature below about 350°

C.

13. A method of forming a ruthenium containing layer on a substrate surface, comprising:

providing an aqueous solution that comprises a perruthenate material, water and a hypochlorite containing material;

adding an amount of an acid to the aqueous solution

adding a solvent to the aqueous solution to form a solvent containing mixture, wherein the solvent is selected from the group consisting of perfluorocarbons, hydroflurocarbons and chlorofluorocarbons;

removing the water from the solvent containing mixture;

separating the ruthenium tetroxide from the solvent containing mixture; and

delivering the ruthenium tetroxide to a substrate positioned on a substrate support in a processing chamber.

14. A method of claim 13, wherein the solvent mixture is a perfluorocarbon, a hydroflurocarbon or a chlorofluorocarbon that is selected from the group consisting of perfluoropentane, perfluorohexane, fluorotrichloromethane and 1,1,2-trichloro-1,2,2-trifluoroethane.

15. A method of claim 13, wherein the substrate support is maintained at a temperature between about 20°

C. and about 350°

C.

16. A method of claim 13, wherein delivering the ruthenium tetroxide to the substrate comprises:

delivering an amount of the ruthenium tetroxide that has been separated from the solvent containing mixture to a vessel;

purging the vessel after the amount of the ruthenium tetroxide has been received in the vessel; and

delivering an amount of the ruthenium tetroxide to the substrate after purging the vessel for a period of time.

17. A method of forming a ruthenium containing layer on a substrate surface, comprising:

forming a ruthenium tetroxide containing mixture that comprises ruthenium tetroxide and a solvent;

collecting the ruthenium tetroxide containing mixture in a first vessel that is located at a first location;

transporting the first vessel to a second location, wherein the first vessel has the ruthenium tetroxide containing mixture disposed therein;

connecting the first vessel to a processing chamber after transporting the first vessel;

separating the ruthenium tetroxide from the solvent; and

removing unwanted contaminants from the ruthenium tetroxide that has been separated from the solvent, wherein removing unwanted contaminants from the ruthenium tetroxide is performed before delivering an amount of the ruthenium tetroxide to a substrate positioned on a substrate support in the processing chamber, wherein the solvent is selected from the group consisting of perfluorocarbons, hydroflurocarbons and chlorofluorocarbons.

18. The method of claim 17, wherein the solvent has a boiling point of less than about 50°

C.

19. The method of claim 17, wherein separating the ruthenium tetroxide from the solvent comprises:

evacuating a region in which the ruthenium tetroxide containing mixture is disposed by use of a pump; and

exposing the ruthenium tetroxide containing mixture to a pressure below atmospheric pressure for a period of time to remove at least a portion of the solvent.

20. The method of claim 19, further comprising cooling at least a portion of the ruthenium tetroxide containing mixture to a temperature less than about 20°

C.

21. The method of claim 17, wherein removing the unwanted contaminants from the ruthenium tetroxide that has been separated from the solvent, comprises:

delivering an amount of the ruthenium tetroxide to a second vessel; and

purging the second vessel after the amount of the ruthenium tetroxide has been delivered to the second vessel.