Solar control coated glass

• US 6,218,018 B1
• Filed: 02/16/1999
• Issued: 04/17/2001
• Est. Priority Date: 08/21/1998
• Status: Expired due to Term

• Current Assignee: Arkema Incorporated (Arkema)
• Original Assignee: ATOFINA Chemicals, Inc. (Arkema)
• Inventors: Russo, David A., Stricker, Jeffrey L., McKown, Clem, Roger, Christophe
• Primary Examiner(s): Jones, Deborah
• Assistant Examiner(s): Miranda, Lymarie
• Application Number:
  US09/249,761
• Time in Patent Office: 791 Days
• Field of Search: 359/580, 359/359, 428/214, 428/432, 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 17/3417 all coatings being oxide coatings
• CPC Class Codes: C03C 2217/211 SnO2
• CPC Class Codes: C03C 2217/24 Doped oxides
• CPC Class Codes: C03C 2217/241 with halides
• CPC Class Codes: C03C 2217/244 with Sb
• CPC Class Codes: C03C 2218/152 by cvd
• CPC Class Codes: Y10T 428/24975 No layer or component greater than 5 mils thick

Abstract

A solar-control glass that has acceptable visible light transmission, absorbs near infrared wavelength light (NIR) and reflects midrange infrared light (low emissivity mid IR) along with a preselected color within the visible light spectrum for reflected light is provided. Also provided is a method of producing the improved, coated, solar-controlled glass. The improved glass has a solar energy (NIR) absorbing layer comprising tin oxide having a dopant such as antimony and a low emissivity control layer (low emissivity) capable of reflecting midrange infrared light and comprising tin oxide having fluorine and/or phosphorus dopant. A separate iridescence color suppressing layer as described in the prior art is generally not needed to achieve a neutral (colorless) appearance for the coated glass, however an iridescence suppressing layer or other layers may be combined with the two layer assemblage provided by the present invention. If desired, multiple solar control and/or multiple low emissivity layers can be utilized. The NIR layer and the low emissivity layer can be separate portions of a single tin oxide film since both layers are composed of doped tin oxide. A method of producing the coated solar control glass is also provided.

Claims

1. A coated, solar control glass having preselected reflected color and having a NIR solar absorbing layer and a low emissivity layer, comprising glass having a SnO₂ coating containing at least two layers with one layer being a solar absorbing layer comprising SnO₂ containing a dopant selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and mixtures thereof and another layer being a low emissivity layer comprising SnO₂ containing a dopant selected from the group fluorine, phosphorus, and mixtures thereof wherein the thickness of the solar absorbing layer is from 80 to 300 nanometers (nm) and the thickness of the low emissivity layer is from 200 to 450 nm, the reflectance of visible light from the coated side of the glass is 6.2% or greater and said preselected reflected color is achieved without the need for a separate iridescence reflected color suppressing layer.

2. The glass of claim 1 wherein the thickness of the solar absorbing layer is from 80 to 300 nanometers (nm) and the thickness of the low emissivity layer is from 200 to 450 nm and said SnO₂ oxide coating is in direct contact with said glass.

3. The glass of claim 1 wherein the thickness of the NIR solar absorbing layer is from 200 to 280 nanometers (nm) and the thickness of the low emissivity layer is from 250 to 350 nm.

6. The coated, solar control glass of claim 1 wherein said solar absorbing layer has a thickness from 220 to 260 nm, a dopant concentration of from 2.5% to 7% by weight in said solar absorbing layer based upon the weight of SnO₂ in said solar absorbing layer, and the low emissivity layer has a thickness of from 280 to 320 nm, a fluorine dopant concentration of from 1% to 5% by weight in said low emissivity layer based upon the weight of SnO₂ in said low emissivity layer, and the coated glass has a Neutral-blue Color for reflected light.

7. The glass of claim 1 wherein the solar absorbing layer is SnO₂ having an antimony dopant within the range of 3% to 6% by weight based upon the weight of SnO₂ tin oxide in the solar control layer, the low emissivity control layer is SnO₂ having a fluorine dopant within range of 1% to 3% dopant by weight based upon the weight of SnO₂ in the low emissivity layer, and the improved glass has a Neutral-blue Color for reflected light.

8. The glass of claim 1 wherein the solar absorbing layer is coated directly onto the glass and the low emissivity layer is coated on top of the solar control layer.

9. The coated solar control glass of claim 1 wherein the preselected reflected color is red.

10. The coated solar control glass of claim 1 wherein the preselected reflected color is yellow.

11. The coated solar control glass of claim 1 wherein the preselected reflected color is green.

12. The coated solar control glass of claim 1 wherein the preselected reflected color is blue.

13. The coated solar control glass of claim 1 wherein the preselected reflected color is Neutral-blue Color.

14. The coated, solar control glass of claim 1 wherein the solar absorbing layer and the low emissivity layer are contained within a single SnO₂ film containing at least two dopants with the first dopant selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and mixtures thereof and the second dopant being fluorine or phosphorus, said first dopant being at a higher concentration then said second dopant at one surface of the film and said first dopant being at a lower concentration then said second dopant at the opposite surface of the film and wherein the portion of said film in proximity with said first surface functions as a solar absorbing layer within said film and wherein the portion of said film in proximity with said opposite surface functions as a low emissivity layer within said film.

15. The coated glass of claim 1 wherein the dopant for the solar absorbing layer is antimony.

16. The coated glass of claim 15 wherein the antimony dopant is obtained from a precursor containing antimony trichloride, antimony pentachloride, antimony triacetate, antimony triethoxide, antimony trifluoride, antimony pentafluoride, or antimony acetylacetonate.

17. The coated glass of claim 1 wherein the dopant for the low emissivity layer is fluorine.

18. The coated glass of claim 17 wherein the fluorine dopant is obtained from a precursor containing trifluoroacetic acid, difluoroacetic acid, monofluoroacetic acid, ethyltrifluoroacetate, ammonium fluoride, ammonium bifluoride, or hydrofluoric acid.

19. The coated glass of claim 1 wherein each of the SnO₂ layers is obtained by pyrolytic decomposition of a tin precursor.

20. The coated glass of claim 19 wherein the tin precursor is selected from the group consisting of monobutyltin trichloride, methyltin trichloride, dimethyltin dichloride, dibutyltin diacetate, and tin tetrachloride.

21. The coated glass of claim 1 wherein the solar absorbing layer is composed of at least two solar absorbing films and the total thickness of the solar absorbing films is form 80 to 320 nm.

22. The coated glass of claim 21 wherein the concentration of dopant in one of said solar absorbing films is different than the concentration of dopant in another of the solar absorbing films.

23. The coated glass of claim 1 wherein the low emissivity layer is composed of at least two low emissivity films, the total thickness of the low emissivity films is form 200 to 450 nm and said first film contains phosphorous as a dopant and said second film contains fluorine as a dopant.

24. The coated glass of claim 23 wherein the concentration of dopant in one of said low emissivity films if different than the concentration of dopant in another of the low emissivity films.

25. The coated glass of claim 1 further comprising a transmitted color modifying quantity of a dopant in said solar absorbing layer.

26. The coated glass of claim 25 wherein said color modifying dopant is fluorine or chlorine.

27. The coated glass of claim 1 further comprising chlorine as a dopant in said solar absorbing layer.

28. A method of producing the coated glass of claim 1 comprising sequentially treating glass at a glass temperature above 400°

C. with;

a first carrier gas containing a source of oxygen, H₂O, a tin precursor and a dopant precursor selected from the group consisting of antimony trichloride, antimony pentachloride, antimony triacetate, antimony triethoxide, antimony trifluoride, antimony pentafluoride, or antimony acetylacetonate; and

,

a second carrier gas containing a source of oxygen, H₂O, a tin precursor and a dopant precursor selected from the group consisting of trifluoroacetic acid, ethyltrifluoroacetate, difluoroacetic acid, monofluoroacetic acid, ammonium fluoride, ammonium bifluoride, and hydrofluoric acid;

to form by pyrolysis a NIR layer comprising SnO₂ containing an antimony dopant and a low emissivity layer comprising SnO₂ containing a fluorine dopant.

29. A method of producing the coated glass of claim 1 comprising sequentially treating glass at a glass temperature above 400°

C. with;

a first carrier gas containing a source of oxygen, H₂O, an organotin precursor and a dopant precursor containing a metal selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, and nickel, and,

a second carrier gas containing a source of oxygen, H₂O, an organotin precursor and a dopant precursor containing fluorine or phosphorus;

to form by pyrolysis a NIR layer comprising SnO₂ containing an antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, or nickel dopant or mixture of dopants and a low emissivity layer comprising SnO₂ containing a fluorine or phosphorus dopant.

30. The method of claim 22 wherein said glass is contacted with the first carrier gas before it is contacted with the second carrier gas.

31. The method of claim 22 wherein said first carrier gas also contains the components of said second carrier gas to produce a product in which the NIR layer contains a fluorine or phosphorus dopant in addition to the dopant of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, or nickel.

32. The method of claim 22 further wherein said first carrier gas also contains a dopant precursor containing fluorine, chlorine or phosphorous.

33. The method of claim 32 wherein said dopant precursor containing fluorine, chlorine or phosphorous is either trifluoroacetic acid, HCl, or phosphorous trichloride.

34. The method of claim 22 further wherein said first carrier gas also contains a film modifier selected from the group consisting of dopant precursor containing fluorine or phosphorous.

35. The coated glass of claim 1 further comprising fluorine dopant in said NIR layer and wherein the reflected color of said glass is different then the transmitted color.

36. The coated glass of claim 26 wherein the reflected color is Neutral Blue Color and the transmitted color is blue.

37. The method of claim 22 wherein said first carrier gas also contains a second dopant precursor containing fluorine or phosphorus or a second dopant precursor containing a metal selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, and nickel.

38. The method of claim 27 wherein said second dopant precursor is selected from the group consisting of trifluoroacetic acid, ethyltrifluoroacetate, difluoroacetic acid, monofluoroacetic acid, ammonium fluoride, ammonium bifluoride, and hydrofluoric acid.

40. The film of claim 32 wherein the fluorine dopant is present in a quantity sufficient to modify the transmitted color of light through the film.

46. The coated glass of claim 1 wherein the percentage of reflectance of visible light from the coated side of the glass is greater than the percentage of reflectance of solar light from the uncoated side of the glass.

48. The coated glass of claim 23 wherein one of said low emissivity layers contains phosphorus as a dopant and another low emissivity layer contains fluorine as a dopant.

49. The coated glass of claim 1 wherein said solar absorbing layer also contains a film modifier dopant selected from the group consisting of fluorine and phosphorus.

4. A coated, solar control glass having a preselected reflected color and having a solar absorbing layer and a low emissivity layer, comprising a SnO₂ film in direct contact with said glass and containing at least two dopants and a difference in the concentration of the dopants from one surface of the film to the opposite surface of the film, said first dopant being selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and mixtures thereof, and said second dopant being fluorine, phosphorus, and mixtures thereof aid first dopant comprising at least 50% of the dopants present at a first surface of said SnO₂ film to form a solar absorbing layer within said SnO₂ film adjacent to said first surface, and said second dopant being present at a concentration at least 50% of the dopant at a second surface of said film opposite said first surface to form a low emissivity layer within said SnO₂ film adjacent to said second surface and the reflectance of visible light from the coated side of the glass is 6.2% or greater.

5. The coated, solar control glass of claim 4 wherein said first dopant is present at a concentration of at least 75% of the dopants present in said SnO₂ film in an area of the film commencing with said first surface and continuing into the SnO₂ film for a depth of at least 80 nm above said first surface, and said second dopant comprises at least 75% of the dopants present in said SnO₂ film in an area of the film commencing with said second surface and continuing into the SnO₂ film at a concentration of at least 75% of the dopants for a depth of at least 80 nm, wherein said area of said SnO₂ film having at least 75% of said second dopant functions as a low emissivity layer, said area of said SnO₂ film having at least 75% of said first dopant functions as a NIR layer and said preselected reflected color is achieved without the need for a separate iridescence reflected color suppressing layer.

47. The coated glass of claim 4 wherein the percentage of reflectance of visible light from the coated side of the glass is greater than the percentage of reflectance of solar light from the uncoated side of the glass.

39. A NIR film comprising tin oxide containing a NIR dopant selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, and nickel and containing a fluorine dopant at an atomic concentration less then the concentration of the NIR dopant.

41. A NIR film comprising tin oxide containing a NIR dopant selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, and nickel and containing a color modifying dopant present in a quantity sufficient to modify the transmitted color of light through the film and selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and fluorine, provided that the selection of color modifying dopant is different then the selection of NIR dopant and when fluorine is the selected dopant its atomic concentration is less then the concentration of the NIR dopant.

42. A coated, solar control glass having Neutral-blue Color for reflected light and having a NIR solar absorbing layer and a low emissivity layer, comprising glass having a coating containing at least two layers with one layer being a solar absorbing layer comprising SnO₂ containing a dopant selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and mixtures thereof and another layer being a low emissivity layer comprising SnO₂ containing a dopant selected from the group fluorine or phosphorus and said Neutral-blue Color for reflected light is achieved without the need for an anti-iridescence reflected color controlling layer.

43. A coated, solar control glass having a color intensity index of 12 or less for reflected light and having a NIR solar absorbing layer and a low emissivity layer, comprising glass having a coating containing at least two layers with one layer being a solar absorbing layer comprising SnO₂ containing a dopant selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and mixtures thereof and another layer being a low emissivity layer comprising SnO₂ containing a dopant selected from the group fluorine or phosphorus and said color intensity index of 12 or less for reflected light is achieved without the need for an anti-iridescence reflected color controlling layer.

44. A coated, solar control glass having C.I.E. 1931 color coordinates x between about 0.285 and 0.310 and y between about 0.295 and 0.325 for reflected light and having a NIR solar absorbing layer and a low emissivity layer, comprising glass having two layers coated thereon with one layer being a solar absorbing layer comprising SnO₂ containing a dopant selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and mixtures thereof and a second layer being a low emissivity layer comprising SnO₂ containing a dopant selected from the group fluorine or phosphorus and said C.I.E. 1931 color coordinates x between about 0.285 and 0.310 and y between about 0.295 and 0.325 for reflected light is achieved without the presence of an anti-iridescence reflected color controlling layer in direct contact with said glass.

45. A coated, solar control glass having a C.I.E. 1931 color coordinates x between about 0.285 and 0.325 and y between about 0.295 and 0.33 for reflected light and having a NIR solar absorbing layer and a low emissivity layer, comprising glass having at least two layers coated thereon, with one layer being a solar absorbing layer comprising SnO₂ containing a dopant selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and mixtures thereof a second layer being a low emissivity layer comprising SnO₂ containing a dopant selected from the group fluorine or phosphorus and said preselected reflected color is achieved without the presence of an anti-iridescence reflected color controlling layer in direct contact with said glass.