Protective layers for sputter coated article

• US 6,833,194 B1
• Filed: 06/16/1999
• Issued: 12/21/2004
• Est. Priority Date: 05/12/1998
• Status: Expired due to Term

• Current Assignee: Vitro Flat Glass LLC (Compagnie De Saint-Gobain)
• Original Assignee: PPG Industries Ohio Incorporated (Nouryon BV)
• Inventors: OʼShaughnessy, Dennis J.
• Primary Examiner(s): MCNEIL, JENNIFER C
• Application Number:
  US09/334,193
• Time in Patent Office: 2,015 Days
• Field of Search: 428/426, 428/432, 428/434, 428/457, 428/472, 428/469, 428/697, 428/699, 428/701, 428/702
• US Class Current: 428/432
• CPC Class Codes: C03C 17/2453 Coating containing SnO2
• CPC Class Codes: C03C 17/36 at least one coating being a metal
• CPC Class Codes: C03C 17/3618 Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
• CPC Class Codes: C03C 17/3626 one layer at least containing a nitride, oxynitride, boronitride or carbonitride
• CPC Class Codes: C03C 17/3639 Multilayers containing at least two functional metal layers
• CPC Class Codes: C03C 17/3644 the metal being silver
• CPC Class Codes: C03C 17/3652 the coating stack containing at least one sacrificial layer to protect the metal from oxidation
• CPC Class Codes: C03C 17/366 Low-emissivity or solar control coatings
• CPC Class Codes: C03C 17/3681 the multilayer coating being used in glazing, e.g. windows or windscreens
• CPC Class Codes: C03C 2217/216 ZnO
• CPC Class Codes: C03C 2217/23 Mixtures
• CPC Class Codes: C03C 2217/24 Doped oxides
• CPC Class Codes: C03C 2217/78 Coatings specially designed to be durable, e.g. scratch-resistant
• CPC Class Codes: C03C 2218/155 by reactive sputtering
• CPC Class Codes: C23C 14/086 of zinc, germanium, cadmium, indium, tin, thallium or bismuth
• CPC Class Codes: C23C 14/3414 Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
• CPC Class Codes: Y10T 428/265 1 mil or less
• CPC Class Codes: Y10T 428/31678 Of metal

Abstract

Tin is added to a zinc cathode target to enhance the sputter efficiency of the target. Films deposited using the cathode, e.g., greater than zero but less than 10 weight percent tin and greater than 90 but less than 100 weight percent zinc improve the chemical durability of a high transmittance, low emissivity coating stack over coating stacks having zinc oxides without tin oxide. High transmittance, low emissivity coating stacks are heated with the heated coating having reduced haze by selecting the thickness of metal primer layer between an infrared reflective film, e.g. a silver film and a dielectric film, e.g., a 52-48 zinc stannate, zinc oxide, tin oxide film or a zinc oxide film. Also disclosed are enhancing films that lower the resistivity of silver films deposited thereon and improve chemical durability of the coating stack.

Claims

1. An infrared reflective coated article comprising:

a substrate;

a dielectric layer sputter deposited over the substrate, the layer comprising a first zinc stannate film deposited over the substrate having zinc in weight percent range of equal to and greater than 10 and equal to and less than 90, and tin in the weight percent range of equal to and less than 90 and equal to and greater than 10, and an electrical enhancing film deposited over the zinc stannate film, the electrical enhancing film selected from the group of films consisting of zinc oxide, tin oxide film and a second zinc stannate film wherein the composition of the first zinc stannate film is at least about 5 weight percent different than the composition of the second zinc stannate film, and

an infrared reflective layer deposited on the dielectric layer,

a metal primer layer over the infrared reflective layer;

a second dielectric layer over the primer layer; and

a protective layer of at least two films selected from the group consisting of metal-containing films which are from different transition metals of Groups 4, 5, 6, or 10 of the Periodic Table of Elements, silicon-containing films, metal and silicon films, films of metal and metal-oxy materials, films of metal and silicon oxy-materials, films of silicon and metal-oxy materials, films of silicon and silicon oxy-materials, and films of metal oxy and silicon oxy materials, where the oxy materials are selected from the group consisting of oxides and oxynitrides, and wherein the protective layer is in a position where it can perform the protective function for providing durability to the dielectric layer, infrared reflective layer, metal primer layer, and second dielectric layer.

2. The coated article of claim 1 wherein the infrared reflective metal is silver and the silver is deposited on the zinc oxide, tin oxide film.

3. The coated article of claim 1 wherein the infrared reflective layer is a silver film and the silver film is deposited on the second zinc stannate film.

4. The coated article of claim 1 wherein the dielectric layer is a first dielectric layer, the infrared reflective layer is a first infrared reflective layer,

the metal primer layer is over the first infrared reflective layer, and

the protective layer is an overcoat over the second dielectric layer.

5. The coated article of claim 4 wherein the second dielectric layer is a zinc stannate film having 10-90 weight percent zinc and 90-10 weight percent tin.

6. The coated article of claim 1 wherein the dielectric layer is a first dielectric layer and the infrared reflective layer is a first infrared reflective layer and further including:

a first metal primer layer over the first infrared reflective metal layer;

a second dielectric layer over the first primer layer;

a second infrared reflective layer over the second dielectric layer;

a second metal primer layer over the second infrared reflective layer;

a third dielectric layer over the second metal primer layer; and

the protective layer is over the third dielectric layer.

7. The coated article of claim 6 wherein at least one of the second and third dielectric layers includes a zinc stannate film having 10-90 weight percent zinc and 90-10 weight percent tin.

8. The coated article of claim 1 wherein the dielectric layer is a first dielectric layer and the infrared reflective layer is a first infrared reflective layer and further including:

a first metal primer layer over the first reflective layer;

a second dielectric layer over the first metal primer layer, the second dielectric layer comprising a first dielectric film and a zinc stannate film defined as a first zinc stannate film, the first zinc stannate film having zinc in the weight percent range of equal to and greater than 10 and equal to and less than 90 and tin in the weight percent range of equal to and greater than 10 and equal to and less than 90, the second dielectric layer deposited over the first metal primer layer;

a second infrared reflective layer deposited over the second dielectric layer;

a second metal primer layer deposited over the second infrared reflective layer;

a third dielectric layer deposited over the second primer layer; and

the protective layer is over the third dielectric layer.

9. The coated article of claim 8 wherein the first dielectric film of the second dielectric layer is selected from the group consisting of a zinc oxide film, a zinc oxide, tin oxide film, and a zinc stannate film defined as a second zinc stannate film, the second zinc stannate film having a composition different than the composition of the first zinc stannate film of the second dielectric layer.

10. The coated article of claim 9 wherein the second zinc stannate film of the second dielectric layer has zinc in the weight percent range of equal to and greater than 60 and equal to and less than 90 and tin in the weight percent of equal to and greater than 10 and equal to and less than 40, and the third dielectric layer is a zinc stannate film.

11. The coated article of claim 1 wherein the dielectric layer is a first dielectric layer and the infrared reflective layer is a first infrared reflective layer and further including:

a first metal primer layer over the first reflective layer;

a second dielectric layer over the first metal primer film;

a second infrared reflective layer over the second dielectric layer;

a second metal primer layer over the second infrared reflecting metal layer;

a third dielectric layer over the second metal primer layer, the third dielectric layer comprising a first dielectric film and a zinc stannate film defined as a first zinc stannate film, the first zinc stannate film having zinc in a weight percent with the range of equal to and greater than 10 and equal to and less than 90 and tin within the weight percent range of equal to and less than 90 and equal to and greater than 10, the third dielectric film deposited over the second metal primer; and

the protective layer overlies the third dielectric film.

12. The coated article of claim 11 wherein the first dielectric film of the third dielectric layer is selected from the group consisting of a zinc oxide film, a zinc oxide, tin oxide film, and a zinc stannate film defined as a second zinc stannate film, the second zinc stannate film having a composition different than the composition of the first zinc stannate film of third dielectric layer.

13. The coated article of claim 12 wherein the second zinc stannate film of the third dielectric layer has zinc in the weight percent range of equal to and greater than 60 and equal to and less than 90 and tin in the weight percent range of equal to and greater than 10 and equal to and less than 40.

14. The coated article of claim 1 wherein the dielectric layer is a first dielectric layer, the infrared reflective layer is a first infrared reflective layer,

the metal primer layer is a first metal primer layer over the first reflective layer, and the

second dielectric layer is over the first metal primer layer, the second dielectric layer comprising a first dielectric film and a zinc stannate film defined as a first zinc stannate film, the first zinc stannate film having zinc in a weight percent within the range of equal to and greater than 10 and equal to and less than 90 and tin within the weight percent range of equal to and less than 90 and equal to and greater than 100, the second dielectric layer deposited over the first metal primer layer, and further comprising;

a second infrared reflective layer over the first zinc stannate film of the second dielectric layer;

a second metal primer layer over the second infrared reflective layer;

a third dielectric layer over the second metal primer layer, the third dielectric layer comprising a first dielectric film and a zinc stannate film defined as a first zinc stannate film, the first zinc stannate film having zinc in a weight percent within the range of equal to and greater than 10 and equal to and less than 90 and tin within the weight percent range of equal to and less than 90 and equal to and greater than 10, the third dielectric layer deposited over the second metal primer layer; and

the protective layer overlies the first zinc stannate film of the third dielectric layer.

15. The coated article of claim 14 wherein the first dielectric film of the second dielectric layer and the first dielectric film of the third dielectric layer each has a film selected from the group consisting of a zinc oxide film, a zinc oxide, tin oxide film, and a second zinc stannate film having a composition different than the composition of the first zinc stannate film in their respective second or third dielectric layer.

16. The coated article of claim 15 wherein the second zinc stannate film of the first and second dielectric layer each include zinc in the weight percent range of equal to and greater than 60 and equal to and less than 90 and tin in the weight percent of equal to and greater than 10 and equal to and less than 40.

17. The coated article of claim 15 wherein the second dielectric layer further includes a third dielectric film over the first zinc stannate film of the second dielectric layer wherein the third dielectric film of the second dielectric layer is a film selected from the group consisting of a zinc oxide film, a zinc oxide, tin oxide film and a zinc stannate film defined as a third zinc stannate film, the third zinc stannate film has a composition different than the composition of the first zinc stannate film of the second dielectric layer closest to the third zinc stannate film.

18. The coated article of claim 15 wherein the second dielectric layer further includes a third dielectric film over the first zinc stannate film of the second dielectric layer, wherein the third dielectric film of the second dielectric layer is selected from the group consisting of a zinc oxide film, a zinc oxide, tin oxide film, and a second zinc stannate film defined as a third zinc stannate film, the third zinc stannate film of the second dielectric layer having a composition different than the composition of the first zinc stannate film of second dielectric layer.

19. The coated article of claim 18 wherein the first and third dielectric films of the second dielectric layer and the first dielectric film of the third dielectric layer each include zinc in the weight percent range of equal to and greater than 60 and equal to and less than 90 and tin in the weight percent of equal to and greater than 10 and equal to and less than 40.

20. The coated article of claim 15 wherein the third dielectric layer further includes a third dielectric film over the first zinc stannate film of the third dielectric layer, wherein the third dielectric film of the third dielectric layer is selected from the group consisting of a zinc oxide film, a zinc oxide, tin oxide film, and a zinc stannate film defined as a third zinc stannate film, the third zinc stannate film of the third dielectric layer having a composition different than the composition of the first zinc stannate film of third dielectric layer.

21. The coated article of claim 14 wherein the second dielectric layer further includes a third dielectric film over the first zinc stannate film of the second dielectric layer.

22. The coated article of claim 14 wherein the substrate is a glass piece and the first zinc stannate film of the first dielectric layer is on the glass piece and has a thickness in the range of 230±

40 Angstroms Å

;

the electrical enhancing film of the first dielectric layer is on the first zinc stannate film of the first dielectric layer and has a thickness in the range of 80±

40 Å

;

the first infrared reflective metal layer is a first silver film deposited on the electrical enhancing film of the first dielectric layer and has a thickness in the range of 110±

30 Å

, the metal primer layer is a titanium film deposited on the first silver layer and has a thickness in the range of 17-26 Å

;

the first dielectric film of the second dielectric layer is deposited on the titanium film and has a thickness in the range of 80±

40 Å

;

the first zinc stannate film of the second dielectric layer is deposited on the first dielectric film of the second dielectric layer and has a thickness in the range of 740±

40 Å

;

the second infrared reflective metal layer is a second silver film deposited on the first zinc stannate film of the second dielectric layer and has a thickness in the range of 110±

38 Å

;

the second primer film is a titanium film deposited on the second silver layer and having a thickness in the range of 18-31 Å

;

the first dielectric film of the third dielectric layer is deposited on the second titanium film and has a thickness in the range of 80±

40 Å

;

the first zinc stannate film layer of the third dielectric layer is deposited on the first dielectric film of the third dielectric layer and has a thickness in the range of 120±

40 Å

, and the protective layer includes a titanium metal film deposited on the first zinc stannate film layer of the third dielectric layer and has a thickness in the range of 29±

3 Å

.

23. The coated article of claim 22 wherein the protective coating further includes a titanium oxide film.

24. The coated article of claim 1 wherein the protective layer has at least two films selected from the group consisting of a metal of titanium, zirconium, niobium, tantalum, chromium, nickel or alloys thereof, a metal oxy material of titanium oxides, titanium oxynitride, zirconium oxides, zirconium oxynitrides, niobium oxides, niobium oxynitrides, tantalum oxide, tantalum oxynitride, chromic oxides, chromic oxynitrides, nickel oxide, nickel oxynitride, silicon oxide, silicon dioxide, and silicon aluminum nitride, and combinations and mixtures of any two or more of these.

25. The coated article of claim 1, wherein the protective layer has a thickness of about 5 to about 60 Å

for the metal or silicon films and about 20 to about 50 Å

for the metal oxy-material or silicon oxy-material films.

26. The coated article of claim 25, wherein the protective layer has a thickness of 10 to about 30 Å

for the metal or silicon films and 30 to 40 Å

for the metal oxy-material or silicon oxy-material films.

27. The coated article of claim 1, wherein the protective layer provides chemical durability.

28. The coated article of claim 1, wherein the protective layer provides mechanical durability.

29. A coated article comprising:

a substrate;

a first dielectric layer over the substrate;

a first infrared reflective layer over the first dielectric layer;

a first metal primer layer over the first infrared reflective layer;

a second dielectric layer over the first metal primer, the second dielectric layer having a first dielectric film selected from the group consisting of a zinc oxide, tin oxide film and a first zinc stannate film, and a second dielectric film having a composition different than the first dielectric film of the second dielectric layer;

a second infrared reflective layer over the second dielectric layer;

a second primer layer over the second reflective layer;

a third dielectric layer over the second metal primer layer; and

a protective layer of at least two films selected from the group consisting of metal-containing films, which are selected from different transition metals of Groups 4, 5, 6 or 10 of the Periodic Table of Elements, silicon-containing films, metal and silicon films, films of metal and metal-oxy materials, films of metal and silicon oxy-materials, films of silicon and metal-oxy materials, films of silicon and silicon oxy-materials, and films of metal oxy and silicon oxy materials, where the oxy-materials are oxides or oxynitrides and wherein the protective layer is in a position where it can perform the protective function for providing durability to the dielectric layers, infrared reflective layers, and metal primer layers.

30. The coated article of claim 29 wherein the first dielectric layer includes a zinc stannate film, the second dielectric film of the second dielectric layer is a zinc stannate film and the third dielectric layer includes a zinc stannate film, each of the zinc stannate films having zinc in the weight percent range of 10-90 and tin in the weight percent range of 90-10.

31. The coated article of claim 30 wherein the first dielectric film of the second dielectric layer is the first zinc stannate film having zinc in the weight percent range of equal to and greater than 90 and equal to and less than 60 and tin in the weight percent range of equal to and greater than 10 and equal to and less than 40.

32. A coated article comprising:

a substrate;

a first dielectric layer over the substrate;

a first infrared reflective layer over the first dielectric layer;

a first metal primer layer over the first infrared reflective layer;

a second dielectric layer over the first metal primer layer;

a second infrared reflective layer over the second dielectric layer;

a second metal primer layer over the second reflective metal layer;

a third dielectric layer having a first dielectric film selected from the group consisting of a zinc oxide film, a zinc oxide, tin oxide film, and a zinc stannate film, and a second dielectric film overlying the first dielectric film, the second dielectric film having a composition different from the first dielectric film; and

the protective layer overlying the third dielectric layer where the protective layer is at least two films selected from the group consisting of;

metal-containing films, which are of different transition metals of Groups 4, 5, 6 or 10 of the Periodic Table of Elements, silicon-containing films, metal and silicon films, films of metal and metal-oxy materials, films of metal and silicon oxy-materials, films of silicon and metal-oxy materials, films of silicon and silicon oxy-materials, and films of metal oxy and silicon oxy materials, where the oxy-materials are selected from the group of oxides or oxynitrides.

33. The coated article of claim 32 wherein the first and second dielectric layers are each a zinc stannate film, and the second dielectric film of the third dielectric layer is a zinc stannate film and each of the zinc stannate films has zinc in the weight percent range of 10-90 and tin in the weight percent range of 90-10.

34. The coated article of claim 33 wherein the first dielectric film of the third dielectric layer has zinc in the weight percent range of equal to and greater than 90 and equal to and less than 60 and tin in the weight percent range of equal to and greater than 10 and equal to and less than 40.

35. A coated article comprising:

a substrate;

a first dielectric layer over the substrate;

a first infrared reflective layer over the first dielectric layer;

a first primer layer over the first reflective metal layer;

a second dielectric layer having a first dielectric film selected from the group consisting of a zinc oxide, tin oxide film and a first zinc stannate film, and a second dielectric film overlying the first dielectric film having a composition different than the first dielectric film of the second dielectric layer;

a second infrared reflective layer over the second dielectric layer;

a second primer layer over the second reflective layer;

a third dielectric layer over the second metal primer layer, the third dielectric layer having a first dielectric film selected from the group consisting of a zinc oxide, tin oxide film and zinc stannate film, and a second dielectric film, the second dielectric film of the third dielectric layer having a composition different than the composition of the first dielectric film of the third dielectric layer; and

the protective layer overlying the third dielectric layer where the protective layer is at least two films selected from the group consisting of;

metal-containing and silicon-containing films, which are different metals, or metal and silicon, or metal and metal-oxy materials, or metal and silicon oxy-materials, or silicon and metal-oxy, or silicon and silicon oxy-materials, or metal oxy and silicon oxy materials, where the oxy materials are selected from the group consisting of oxides and oxynitrides and where the metal is selected from the group consisting of a transition metal of Groups 4, 5, 6 or 10 of the Periodic Table of Elements.

36. The coated article of claim 35 wherein the first dielectric layer, the second dielectric film of the second and third dielectric layers are each a zinc stannate film having zinc in the weight percent range of 10-90 and tin in the weight percent range of 90-10.

37. The coated article of claim 36 wherein the first dielectric film of the second and third dielectric layers are each a zinc stannate film having zinc in the weight percent range of equal to and greater than 90 and equal to and less than 60 and tin in the weight percent range of equal to and greater than 10 and equal to and less than 40.

38. The coated article of claim 36 wherein the coated article is a transparency.

39. The coated article of claim 38 wherein the coated article is an automotive transparency.

40. The coated article of claim 39 wherein the automobile transparency is an automotive windshield having a pair of glass sheets laminated together and one of the sheets is fabricated from the substrate having the coating.

41. An infrared reflective coated article comprising:

a glass substrate;

a first dielectric layer over the substrate, the first dielectric layer comprising a dielectric film over a zinc stannate film, wherein the zinc stannate film of the first dielectric layer has a thickness in the range of 230±

40 Angstroms Å and

has zinc in weight percent range of equal to and greater than 10 and equal to and less than 90 and tin in the weight percent range of equal to and less than 90 and equal to and greater than 10, and the dielectric film of the first dielectric layer has a thickness in the range of 80±

40 Å and

is different from the zinc stannate film of the first dielectric layer;

a first infrared reflective layer over the first dielectric layer, wherein the first infrared reflective metal layer is a first silver film and has a thickness in the range of 110±

30 Å

;

a first metal primer layer over the first infrared reflective layer, wherein the metal primer layer is a titanium film and has a thickness in the range of 17-26 Å

;

a second dielectric layer over the first metal primer layer, the second dielectric layer comprising a zinc stannate film over a dielectric film, wherein the dielectric film of the second dielectric layer has a thickness in the range of 80±

40 Å

, the zinc stannate film of the second dielectric layer has a thickness in the range of 740±

40 Å and

has zinc in a weight percent within the range of equal to and greater than 10 and equal to and less than 90 and tin within the weight percent range of equal to and less than 90 and equal to and greater than 10, and the dielectric film of the second dielectric layer is different from the zinc stannate film of the second dielectric layer;

a second infrared reflective layer over the second dielectric layer, wherein the second infrared reflective metal layer is a second silver film and has a thickness in the range of 110±

38 Å

;

a second metal primer layer over the second infrared reflective layer, wherein the second primer film is a titanium film and has a thickness in the range of 18-31 Å

;

a third dielectric layer over the second metal primer layer, the third dielectric layer comprising a zinc stannate film over a dielectric film, wherein the dielectric layer of the third dielectric layer has a thickness in the range of 80±

40 Å

, the zinc stannate film of the third dielectric layer has a thickness in the range of 120±

40 Å and

has zinc in a weight percent within the range of equal to and greater than 10 and equal to and less than 90 and fin within the weight percent range of equal to and less than 90 and equal to and greater than 10, and the dielectric film of the third dielectric layer is different from the zinc stannate film of the third dielectric layer; and

a protective layer of titanium metal film over the third dielectric layer and having a thickness in the range of 29±

3 Å

.