Metal oxide films

• US 4,065,600 A
• Filed: 05/18/1971
• Issued: 12/27/1977
• Est. Priority Date: 05/20/1970
• Status: Expired due to Term

• Current Assignee: Triplex Safety Glass Co. (Nippon Sheet Glass Company Limited)
• Original Assignee: Triplex Safety Glass Co. (Nippon Sheet Glass Company Limited)
• Inventors: Hiscutt, Robert, King, Robert David, Molineux, Peter
• Primary Examiner(s): Vertiz, O. R.
• Assistant Examiner(s): Langel, Wayne A.
• Application Number:
  US05/144,541
• Time in Patent Office: 2,415 Days
• Field of Search: 204/192, 204/192 P, 428/432, 428/539
• US Class Current: 428/432
• CPC Class Codes: C23C 14/0036 Reactive sputtering
• CPC Class Codes: H01B 1/00 Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors

Abstract

In a method of depositing a transparent electrically conductive metal oxide coating by reactive sputtering onto the surface of a substrate, the substrate is supported, in spaced relationship with a cathode which is to be sputtered, in a vacuum chamber containing an atmosphere comprising an inert gas and a controlled oxygen concentration at a selected total pressure. The substrate is heated prior to sputtering to a selected elevated temperature, and reactive sputtering is caused by applying a selected negative potential relative to the substrate. The oxygen in the atmosphere is provided and maintained at a selected concentration, and the heating of said substrate is controlled during sputtering to maintain the substrate temperature substantially constant at the selected temperature during substrate heating caused by sputtering. The selected values of the oxygen concentration substrate temperature, vacuum chamber pressure, and cathode potential are so chosen that the deposited coating is haze-free, and its specific electrical resistivity lies at or close to the minimum of the curve which is obtained by plotting specific electrical resistivity against oxygen concentration while maintaining the substrate temperature, vacuum chamber pressure and cathode potential all constant at the selected values. Glass articles with stable, transparent and haze-free coatings having acceptable resistance are produced by the method.

Claims

1. A method of depositing a transparent electrically conductive metal oxide coating by reactive sputtering onto the surface of a substrate, wherein:

the substrate is supported, in spaced relationship with a cathode which is to be sputtered, in a vacuum chamber containing an atmosphere comprising an inert gas and a controlled oxygen concentration at a selected reduced total pressure, the substrate is heated prior to sputtering to a selected elevated temperature, and reactive sputtering is caused by applying a selected negative potential to the cathode relative to the substrate, the oxygen in the atmosphere being provided and maintained at a selected concentration, and the heating of said substrate being controlled during sputtering to maintain said substrate temperature substantially constant at said selected temperature during heating of said substrate caused by sputtering, the selected values of the oxygen concentration, substrate temperature, vacuum chamber pressure, and cathode potential being so chosen that the deposited coating is haze-free, and its specific electrical resistivity lies at or close to the minimum of the curve which is obtained by plotting specific electrical resistivity against oxygen concentration while maintaining the substrate temperature, vacuum chamber pressure and cathode potential all constant at said selected values.

2. The method according to claim 1 wherein the substrate is a sheet of soda-lime-silica glass.

3. The method according to claim 2 wherein the glass is toughened before having said coating sputtered therein.

4. The method of claim 1 wherein the cathode is an alloy of a base metal having an atomic number of from 48 to 52 and another compatible metal.

5. The method of claim 1 wherein the cathode is an alloy of a base metal having an atomic number of from 48 to 52 and another compatible metal having a valency difference of 1 or 2 with respect to the base metal.

6. The method of claim 1 wherein the cathode is an indium/tin alloy comprising between 50 and 98% indium and between 2 and 50% tin.

7. The method of claim 1 wherein the cathode is an indium/tin alloy comprising between 80 and 90% indium and between 10 and 20% tin.

8. The method according to claim 1 wherein the cathode is formed from an alloy selected from indium/tin, indium/germanium, indium/phosphorus, and indium/tellurium.

9. The method of claim 1 wherein the potential difference between the cathode and the substrate is in the range of from -1kV to -5kV.

10. The method of claim 1 wherein the potential difference between the cathode and the substrate is in the range of from -2kV to -3.5kV.

11. The method of claim 1 wherein said selected temperature of said substrate is in the range of from 200°

to 350°

C.

12. The method of claim 1 wherein said selected temperature of said substrate is in the range of from 270°

to 320°

C.

13. The method of claim 1 wherein said selected value of oxygen concentration is in the range of from 1 to 9% by volume present within the space between the cathode and the substrate surface.

14. The method of claim 1 wherein said selected value of oxygen concentration is in the range of from 1 to 6% by volume present within the space between the cathode and the substrate surface.

15. The method of claim 1 wherein said selected value of oxygen concentration is in the range of from 1.6 to 1.9% by volume and said selected temperature of said substrate is in the range of from 280°

and 300°

C.

16. The method of claim 1 wherein said selected vacuum chamber pressure is in the range of from 10 microns Hg to 100 microns Hg.

17. The method of claim 1 wherein said selected vacuum chamber pressure is from 40 microns Hg to 90 microns Hg.

18. The method according to claim 1 wherein the substrate is a refractory os siliceous material.

19. The method according to claim 1 wherein the substrate is selected from porcelain, silica and mica.

20. An article with a transparent and haze-free, electrically conductive metal oxide coating having a specific electrical resistivity below 10 ×

10^-4 ohm.cm. applied thereon by a process according to claim 1.

21. An article according to claim 20 wherein the coating has a specific electrical resistivity between 2.5 ×

10^-4 ohm. cm. and 10 ×

10^-4 ohm.cm.

22. An article with a transparent and haze-free, electrically conductive metal oxide coating having a specific electrical resistivity below 20 ×

10^-4 ohm. cm. applied thereon by a process according to claim 1.

23. A glass article with a stable, transparent and haze-free, electrically conductive coating having a resistance in the range of from 2 ohm/sq. to 100 ohm/sq. applied thereon by a process according to claim 1.

24. A method of depositing a transparent electrically conductive metal oxide coating onto the surface of a glass substrate by reactive sputtering, the process comprising the following steps:

supporting the substrate in a chamber in spaced relationship with a cathode of an alloy which is to be sputtered,

evacuating the chamber,

heating the surface of the substrate to a selected temperature in the range of from 200°

to 350°

C before commencing sputtering,

providing an atmosphere in the chamber comprising an inert gas and a controlled oxygen concentration and maintaining the pressure of the atmosphere in the chamber at a selected value of from 10 to 100 microns Hg,

maintaining the oxygen in the space between the cathode and the substrate at a selected oxygen concentration within the range of 1 to 9% by volume,

causing deposition of a metal oxide film on the substrate by reactive sputtering by applying a negative potential to the cathode selected such that the potential difference between cathode and substrate is in the range of from -1kV to -5kV, and

controlling the heating of the surface of the substrate during sputtering to maintain the substrate temperature substantially constant at said selected temperature,

the selected values of the oxygen concentration, substrate temperature, vacuum chamber pressure, and cathode potential being so chosen that the deposited coating is haze-free, and its specific electrical resistivity lies at or close to the minimum of the curve which is obtained by plotting specific electrical resistivity against oxygen concentration while maintaining the substrate temperature, vacuum chamber pressure and cathode potential all constant at said selected values.

25. The method according to claim 24 wherein the substrate is a sheet of soda-lime-silica glass.

26. The method according to claim 25 wherein the glass is toughened before having said coating sputtered therein.

27. The method of claim 24 wherein the cathode is an alloy of a base metal having an atomic number of from 48 to 52 and another compatible metal.

28. The method of claim 24 wherein the cathode is an alloy of a base metal having an atomic number of from 48 to 52 and another compatible metal having a valency difference of 1 or 2 with respect to the base metal.

29. The method of claim 24 wherein the cathode is an indium/tin alloy comprising between 50 and 98% indium and between 2 and 50% tin.

30. The method of claim 24 wherein the cathode is an indium/tin alloy comprising between 80 and 90% indium and between 10 and 20% tin.

31. The method according to claim 24 wherein the cathode is formed from an alloy selected from indium/tin, indium/germanium, indium/phosphorus, and indium/tellurium.

32. The method of claim 24 wherein the potential difference between the cathode and the substrate is in the range of from -2kV to -3.5kV.

33. The method of claim 24 wherein said selected temperature of said substrate is in the range of from 270°

to 320°

C.

34. The method of claim 24 wherein said selected value of oxygen concentration is in the range of from 1 to 6% by volume present within the space between the cathode and the substrate surface.

35. The method of claim 24 wherein said selected value of oxygen concentration is in the range of from 1.6 to 1.9% by volume and said selected temperature of said substrate is in the range of from 280°

and 300°

C.

36. The method of claim 24 wherein said selected vacuum chamber pressure is from 40 microns Hg to 90 microns Hg.

37. The method according to claim 24 wherein the substrate is a refractory or siliceous material.

38. The method according to claim 24 wherein the substrate is selected from porcelain, silica and mica.

39. A glass article with a transparent and haze-free, electrically conductive metal oxide coating having a specific electrical resistivity below 10 ×

10^-4 ohm. cm. applied thereon by a process according to claim 24.

40. A glass article according to claim 39 wherein the coating has a specific electrical resistivity between 2.5 ×

10^-4 ohm. cm. and 10 ×

10^-4 ohm.cm.

41. A glass article with a transparent and haze-free, electrically conductive metal oxide coating having a specific electrical resistivity below 20 ×

10^-4 ohm. cm. applied thereon by a process according to claim 24.

42. A glass article with a stable, transparent and haze-free, electrically conductive coating having a resistance in the range of from 2 ohm/sq. to 100 ohm/sq. applied thereon by a process according to claim 24.