Anisotropic liquid phase photochemical copper etch

• US 5,279,702 A
• Filed: 09/30/1992
• Issued: 01/18/1994
• Est. Priority Date: 09/30/1992
• Status: Expired due to Term

• Current Assignee: Texas Instruments, Inc.
• Original Assignee: Texas Instruments, Inc.
• Inventors: Douglas, Monte A.
• Primary Examiner(s): Powell, William A.
• Application Number:
  US07/954,087
• Time in Patent Office: 475 Days
• Field of Search: 156/635, 156/643, 156/656, 156/659.1, 156/666, 156/901, 156/902
• US Class Current: 216/94
• CPC Class Codes: C23F 1/02 Local etching
• CPC Class Codes: H01L 21/32134 by liquid etching only
• CPC Class Codes: H05K 3/06 the conductive material being removed chemically or electrolytically, e.g. by photo-etch process semi-additive methods H05K3/108

Abstract

A copper substrate 30 is immersed in a liquid 34 (e.g. 0.1 molar concentration hydrochloric acid) and illuminated with collimated radiation 24 (e.g. collimated visible/ultraviolet radiation) produced by a radiation source 20 (e.g. a 200 Watt mercury xenon arc lamp). A window 26 which is substantially transparent to the collimated radiation 24 allows the radiated energy to reach the copper substrate 30. An etch mask 32 may be positioned between the radiation source 20 and the substrate 30 (preferably the mask is also in the liquid). The copper substrate 30 and liquid 34 may be maintained at a nominal temperature (e.g. 25° C.). Without illumination, the copper is not appreciably etched by the liquid. Upon illumination the etch rate is substantially increased. A further aspect is the addition of a passivant (e.g. iodine) to the liquid which forms a substantially insoluble passivation layer 36 on the substrate which is removed or partially removed by the radiation 24. Sidewalls 40 are protected from the etchant by vertical passivation layers 42, further increasing the difference between the illuminated and unilluminated etch rates.

Claims

1. A method to anisotropically etch copper, said method comprising:

(a) submersing a surface of said copper in a liquid; and

(b) illuminating portions of said surface with radiation to produce illuminated areas and

substantially unilluminated areas of said surface, wherein said illuminated areas are etched at a substantially greater rate than said unilluminated areas.

2. The method according to claim 1, wherein said illuminated areas are at a temperature substantially the same as the temperature of said unilluminated areas.

3. The method according to claim 1, wherein said liquid contains hydrochloric acid.

4. The method according to claim 1, wherein said liquid is H₂ O.

5. The method according to claim 1, wherein said radiation is produced by a mercury/xenon arc lamp.

6. The method according to claim 1, wherein said copper is on the surface of a VLSI semiconductor substrate.

7. The method according to claim 1, wherein said copper is part of in integrated circuit.

8. The method according to claim 1, wherein the direction of propagation of said radiation is substantially orthogonal to said surface.

9. The method according to claim 1, wherein said liquid is acidic.

10. The method according to claim 1, wherein said liquid is a salt solution.

11. The method according to claim 1, wherein the intensity of said radiation varies with time.

12. The method according to claim 1, wherein said liquid is made to flow with respect to said copper.

13. The method according to claim 1, wherein said radiation is monochromatic.

14. The method according to claim 1, wherein an etch mask is interposed between the source of said radiation and said surface, whereby portions of said surface are not illuminated.

15. The method according to claim 14, wherein said etch mask is comprised of silicon dioxide.

16. The method according to claim 14, wherein said etch mask is comprised of silicon nitride.

17. The method according to claim 14, wherein said etch mask is comprised of one or more noble metals.

18. The method according to claim 14, wherein said etch mask is photoresist.

19. The method according to claim 1, wherein a passivant is added to said liquid, said passivant forming a passivation layer on said surface, said passivation layer being substantially insoluble in said unilluminated areas but substantially removed from said illuminated areas by said radiation, whereby the etch rate in said illuminated areas is substantially greater than the etch rate in said unilluminated areas.

20. The method according to claim 19, wherein said passivant is iodine.

21. The method according to claim 19, wherein said liquid contains hydrochloric acid.

22. A method to etch copper on a VLSI semiconductor substrate, said method comprising submersing said copper in a liquid and illuminating said copper with radiation.

23. A method to anisotropically etch copper on an integrated circuit, said method comprising:

(a) submersing a surface of said copper in 0.1% molar concentration hydrochloric acid; and

(b) illuminating portions of said surface with radiation,

whereby said illuminated portions of said surface are etched at a substantially greater rate than the unilluminated portions of said surface.

24. The method according to claim 23, wherein 0.019% molar concentration iodine is added to said liquid.