Methods for reducing metal oxide surfaces to modified metal surfaces using a gaseous reducing environment

• US 9,070,750 B2
• Filed: 03/06/2013
• Issued: 06/30/2015
• Est. Priority Date: 03/06/2013
• Status: Active Grant

• Current Assignee: Novellus Systems Incorporated (Lam Research Corporation)
• Original Assignee: Novellus Systems Incorporated (Lam Research Corporation)
• Inventors: Spurlin, Tighe A., Lambert, Darcy E., Singhal, Durgalakshmi, Antonelli, George Andrew
• Primary Examiner(s): PHAM, THANHHA S
• Application Number:
  US13/787,499
• Publication Number:
  US 20140256127A1
• Time in Patent Office: 846 Days
• Field of Search: 438/622, 438/625, 438627-629, 438/687
• US Class Current: 1/1
• CPC Class Codes: C23C 18/1619 Apparatus for electroless plating
• CPC Class Codes: C23C 18/1632 Features specific for the apparatus, e.g. layout of cells and of its equipment, multiple cells
• CPC Class Codes: C23C 18/1653 Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
• CPC Class Codes: C23C 18/1851 of surfaces of non-metallic or semiconducting in organic material
• CPC Class Codes: C23C 18/1865 Heat
• CPC Class Codes: C23C 18/1868 Radiation, e.g. UV, laser
• CPC Class Codes: C25D 17/001 Apparatus specially adapted for electrolytic coating of wafers, e.g. semiconductors or solar cells
• CPC Class Codes: H01J 37/32357 Generation remote from the workpiece, e.g. down-stream
• CPC Class Codes: H01L 21/02063 the processing being the formation of vias or contact holes
• CPC Class Codes: H01L 21/02068 during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
• CPC Class Codes: H01L 21/67115 mainly by radiation
• CPC Class Codes: H01L 21/67207 comprising a chamber adapted to a particular process
• CPC Class Codes: H01L 21/76861 Post-treatment or after-treatment not introducing additional chemical elements into the layer
• CPC Class Codes: H01L 21/76862 Bombardment with particles, e.g. treatment in noble gas plasmas; UV irradiation
• CPC Class Codes: H01L 21/76873 for electroplating

Abstract

Method and apparatus for reducing metal oxide surfaces to modified metal surfaces are disclosed. Metal oxide surfaces are reduced to form a film integrated with a metal seed layer on a substrate by exposing the metal oxide surfaces to a reducing gas atmosphere comprising radicals of a reducing gas species. The radicals of the reducing gas species can form from exposing the reducing gas species to ultraviolet radiation and/or a plasma. The substrate is maintained at a temperature below a temperature that produces agglomeration of the metal seed layer during exposure to the reducing gas atmosphere, such as below 150° C. for copper. In some embodiments, the reducing gas species can include at least one of hydrogen, ammonia, carbon monoxide, diborane, sulfite compounds, carbon and/or hydrocarbons, phosphites, and hydrazine.

Claims

1. A method of preparing a substrate. with a metal seed layer for plating,the method comprising:

receiving a substrate having the metal seed layer on a plating surface of the substrate, wherein a portion of the metal seed layer has been converted to an oxide of the metal; and

exposing at least the oxide of the metal to a radicalized reducing gas atmosphere, wherein the reducing gas atmosphere comprises radicals of reducing gas species, and wherein exposure to the reducing gas atmosphere reduces the oxide of the metal to the metal in the form of a film integrated with the seed layer;

cooling the substrate using an active cooling system during exposure to the radicalized reducing gas atmosphere to maintain a substrate temperature below a temperature that produces agglomeration of the metal seed layer;

transferring the substrate to a plating bath containing a plating solution; and

plating metal onto the metal seed layer using the plating solution.

2. The method of claim 1, wherein the metal comprises copper.

3. The method of claim 2, wherein the substrate is maintained at a temperature below about 150°

C.

4. The method of claim 2, wherein the substrate temperature is maintained at a temperature below about 100°

C. by an actively cooled pedestal.

5. The method of claim 1 wherein the thickness of the metal seed layer is less than about 100 Å

.

6. The method of claim 1, wherein the plating surface comprises recesses having height to width aspect ratios of greater than about 5:

1.

7. The method of claim 1, wherein the metal seed layer includes a semi-noble metal that serves as a diffusion barrier.

8. The method of claim 1, wherein the substrate comprises a damascene template, wherein the damascene template comprises vias with height to width aspect ratios of greater than about 5:

1.

9. The method of claim 1, wherein the reducing gas species comprises at least one of hydrogen, ammonia, carbon monoxide, diborane, sulfite compounds, carbon and/or hydrocarbons, phosphites, and hydrazine.

10. The method of claim 1, further comprising exposing the reducing gas species to ultraviolet radiation to form radicals of the reducing gas species.

11. The method of claim 10, wherein the wavelength of the ultraviolet radiation is between about 100 nm and about 400 nm.

12. The method of claim 11, wherein the wavelength of the ultraviolet radiation is between about 120 nm and about 170 nm,

13. The method of claim 10, wherein the intensity of the ultraviolet radiation is between about 1 W/cm² and about 10 W/cm².

14. The method of claim 1, further comprising exposing the reducing gas species to a remote plasma to form radicals of the reducing gas species.

15. The method of claim 14, wherein the remote plasma comprises a radio frequency (RF) power source or microwave power source.

16. The method of claim 1, wherein the exposing step is performed in a chamber having a pressure between about 0.1 Torr and about 50 Torr.

17. The method of claim 1, wherein the exposing step is performed in a chamber having a temperature between about 10°

C. and about 500°

C.

18. The method of claim 1, wherein the exposing step comprises introducing each of the reducing gas species at a flow rate between about 1 sccm and about 100,000 sccm.

19. The method of claim 1, wherein the exposing step is performed in a chamber for a duration between about 1 second and about 60 minutes.

20. The method of claim 1, wherein the substrate is maintained under an atmosphere substantially free of oxygen while transferring the substrate to the plating bath.