Multi-layer interference coatings

• US 6,399,228 B1
• Filed: 03/12/1999
• Issued: 06/04/2002
• Est. Priority Date: 09/23/1996
• Status: Expired due to Term

• Current Assignee: Qinetiq Limited (QinetiQ Group PLC)
• Original Assignee: Qinetiq Limited (QinetiQ Group PLC)
• Inventors: Simpson, John
• Primary Examiner(s): Jones, Deborah
• Assistant Examiner(s): MCNEIL, JENNIFER C
• Application Number:
  US09/254,717
• Time in Patent Office: 1,180 Days
• Field of Search: 428/432, 428/428, 428/469, 428/472, 428/696, 428/701, 428/702, 428/446, 428/448, 428/402, 428/403, 428/698, 359/360, 359/585, 359/588, 359/586, 359/589
• US Class Current: 428/699
• CPC Class Codes: B05D 5/065 having colour interferences or colour shifts or opalescent looking, flip-flop, two tones
• CPC Class Codes: C03C 17/36 at least one coating being a metal
• CPC Class Codes: C03C 17/3615 Coatings of the type glass/metal/other inorganic layers, at least one layer being non-metallic
• 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 17/3642 the multilayer coating containing a metal layer
• CPC Class Codes: C03C 17/3649 made of metals other than 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 17/3657 the multilayer coating having optical properties
• CPC Class Codes: C03C 17/3676 specially adapted for use as electromagnetic shield
• CPC Class Codes: C03C 2217/94 Transparent conductive oxide layers [TCO] being part of a multilayer coating
• CPC Class Codes: C09D 7/00 Features of coating compositions, not provided for in group C09D5/00 driers C09F9/00; Processes for incorporating ingredients in coating compositions
• CPC Class Codes: G02B 1/10 Optical coatings produced by application to, or surface treatment of, optical elements G02B1/08 takes precedence
• CPC Class Codes: G02B 1/116 including electrically conducting layers
• CPC Class Codes: G02B 5/288 comprising at least one thin film resonant cavity, e.g. in bandpass filters

Abstract

A multi layer interference coating comprising at least one multi layer stack deposited on a reflective layer (9), wherein each multi layer stack comprises a first dielectric layer (11), a layer of asbsorbing material (10) and a second layer of dielectric material (11) arranged in series and having a reflectance spectrum in the infrared region comprising at least one maximum. The dielectric layers are of equal optical thickness and typically are of the same material. The multi layer structure of the coating is such that incident electromagnetic radition, for which odd multiples of half wavelengths correspond to the optical thickness of the multi layer coating at the incident wavelength do not propagate within the coating and reflection at these wavelengths, is suppressed. Coatings may therefore be designed to have a near satured color in the visible wavelength spectrum. The reflective layer may be a metal or a conducting oxide, a conducting nitride, a conducting silicide or a conducting sulphide. The absorbing layers may be Cr, V, Pd, Ni, Pt, conducting oxides, or substoichiometric metal oxides, such as TiO_x. In one form of the coating, where a non-metal absorber is used, the second dielectric layer may be removed in at least one of the multi layer stacks. The coating may be incorporated in a system for verifying the authenticity of an article.

Claims

1. A multi layer interference device having a reflectance spectrum comprising at least one maximum comprising;

at least one multilayer stack,

a reflective layer having at least one surface for carrying said at least one multi layer stack,

said at least one multi layer stack comprises a first layer of dielectric material, a layer of absorbing material and a second layer of dielectric material arranged in series with the layer of absorbing material situated between the first and second layers of dielectric material,

wherein the second layer of dielectric material has substantially the same optical thickness as the first layer of dielectric material at a wavelength substantially corresponding to a maximum in the reflectance spectrum and wherein the layer of absorbing material has a refractive index n and an optical constant k, such that incident electromagnetic radiation, having a wavelength at which odd multiples of half wavelengths substantially correspond to the optical thickness of the at least one multi layer stack at said wavelength, is substantially absorbed within the device,

wherein the layer of absorbing material is a conductive substoichiometric metal oxide and in that the device has a reflectance spectrum in the infrared wavelength region.

2. The device of claim 1 wherein the first dielectric material is the same as the second dielectric material.

3. The device of claim 1 wherein at least one of the first or second dielectric materials is any one of titanium oxide (TiO₂), magnesium fluoride (MgF₂), zinc sulphide (ZnS), zinc selenide (ZnSe), silicon (Si), germanium (Ge) or barium fluoride (BaF₂).

4. The device of claim 3 wherein the n/k ratio of the absorbing material is between 0.7 and 1.3 in the infrared wavelength region.

5. The device of claim 4 wherein the n/k ratio of the absorbing material is substantially equal to 1 in the infrared wavelength region.

6. The device of claim 5 wherein the reflective layer is a metal.

7. The device of claim 5 wherein the reflective layer is any one of a conducting oxide, a conducting nitride, a conducting silicide or a conducting sulphide.

8. The device of claim 1 wherein the substoichiometric metal oxide absorbing material is of the same material as the layer of dielectric material.

9. The device of claim 8 wherein the substoichiometric metal oxide is TiO_x and the dielectric material is TiO₂.

10. The device of claim 1 wherein the reflective layer has two opposite facing surfaces wherein at least one multi layer stack is deposited on each of the two opposite facing surfaces such that the device has a substantially symmetric structure about the reflective layer.

11. The device of claim 1 wherein the device is in the form of a thin film.

12. The device of claim 11 wherein the thin film is flaked into fragments.

13. A moulded article incorporating the fragments of thin film of the device according to claim 12.

14. A paint or ink incorporating the fragments of thin film of the device according to claim 12.

15. An article, wherein said paint or ink of the device according to claim 14 is applied to the surface of said article.

16. An article having a label, said label having said paint or ink of the device according to claim 14 applied thereto.

17. The device of claim 1 wherein the reflective layer is a reflecting particulate substrate.

18. The device of claim 17 wherein the particulate substrate is substantially spherical.

19. The device of claim 1 wherein the reflective layer is deposited on a substantially non-reflecting particulate substrate.

20. A system for marking an article and checking its authenticity comprising;

the device of claim 1 wherein the device is applied to the article to be authenticated,

an illuminator for illuminating the device with incident radiation comprising one or more wavelengths wherein one or more of the wavelengths substantially correspond to a maximum or a minimum in the reflectance spectrum of the device and

a detector for detecting radiation reflected from the device at one or more of the wavelengths,

whereby the detection of the reflected radiation provides an indication of the authenticity of the article.

21. The system of claim 20, whereby a comparison of the reflected radiation at two or more wavelengths provides an indication of the authenticity of the article.

22. The system of claim 20 wherein the detector for detecting infrared radiation reflected from the device is a thermal imager.

23. The system of claim 20 wherein the detector for detecting infrared radiation reflected from the device is a spectrophotometer.

24. A multi layer interference device, having a reflectance spectrum in the infrared wavelength region comprising at least one maximum, comprising;

at least one multilayer stack,

a reflective layer having at least one surface for carrying said at least one multi layer stack,

wherein said at least one multi layer stack comprises a first layer of dielectric material, a layer of absorbing material and a second layer of dielectric material arranged in series with the layer of absorbing material situated between the first and second layers of dielectric material,

wherein the second layer of dielectric material has substantially the same optical thickness as the first layer of dielectric material at a wavelength substantially corresponding to a maximum in the reflectance spectrum and wherein the layer of absorbing material has a refractive index n and an optical constant k, such that incident electromagnetic radiation, having a wavelength at which odd multiples of half wavelengths substantially correspond to the optical thickness of said at least one multi layer stack at said wavelength, is substantially absorbed within the device and wherein the layer of absorbing material is any one of a conducting oxide, a conducting nitride, a conducting silicide or a conducting sulphide for which the n/k ratio is substantially equal to 1 in the infrared wavelength region.

25. The device of claim 24 wherein the reflective layer is a metal.

26. The device of claim 24 wherein the reflective layer is any one of a conducting oxide, a conducting nitride, a conducting silicide or a conducting sulphide.

27. The device of claim 24 wherein the absorbing material is substantially the same material as the reflective layer.

28. The device of claim 24 wherein the absorbing material is any one of indium tin oxide (ITO), doped tin oxide or titanium nitride (TiN).

29. The device of claim 24 wherein the layer of absorbing material is vanadium dioxide (VO₂) and the reflectance spectrum of the device may be varied with temperature.

30. A system for covertly marking an article and checking its authenticity comprising;

the device of claim 29, wherein the device is applied to the article to be authenticated;

a temperature control for varying the temperature of the device such that the reflectance of the device at one or more wavelengths may be varied as the temperature is varied;

an illuminator for illuminating the device with infrared radiation comprising one or more wavelengths substantially corresponding to one or more of the wavelengths at which the reflectance varies and

a detector for detecting infrared radiation reflected from the device at one or more wavelengths at which the reflectance varies,

whereby a comparison of the reflected radiation before and after the temperature of the device is varied provides an indication of the authenticity of the article.

31. The system of claim 30 wherein the means for illuminating the device and the temperature control is a single laser.

32. The device of claim 24 wherein the absorbing material is substoichiometric vanadium dioxide (VO₂₋

x) and the reflectance spectrum of the device may be varied with temperature.

33. The device of claim 24 wherein the absorbing material is doped vanadium dioxide and the reflectance spectrum of the device may be varied with temperature.

34. A multi layer interference device, having a reflectance spectrum in the infrared wavelength region comprising at least one maximum, comprising:

at least one multilayer stack,

a reflective layer having at least one surface for carrying said at least one multi layer stack,

said at least one multi layer stack comprises a layer of dielectric material and a layer of absorbing material, wherein the layer of absorbing material has a refractive index n and an optical constant k, such that incident electromagnetic radiation, having a wavelength at which odd multiples of quarter wavelengths substantially correspond to the optical thickness of said at least one multi layer stack at said wavelength, is substantially absorbed within the device,

wherein the layer of absorbing material is a non-metal absorbing material.

35. The device of claim 34 wherein the reflective layer is a metal.

36. The device of claim 34 wherein the reflective layer is any one of a conducting oxide, a conducting nitride, a conducting silicide or a conducting sulphide.

37. The device of claim 34 wherein the layer of non-metal absorbing material is any one of a conducting oxide, a conducting nitride or a conducting silicide for which the n/k ratio is substantially equal to 1 in the infrared wavelength region.

38. The device of claim 37 wherein the non-metal absorbing material is any one of ITO, doped tin oxide or TiN.

39. The device of claim 37 wherein the non-metal absorbing material is vanadium oxide (VO₂) and wherein the reflectance spectrum may be varied with temperature.

40. The device of claim 37 wherein the non-metal absorbing material is substoichiometric vanadium oxide (VO₂) and wherein the reflectance spectrum may be varied with temperature.

41. The device of claim 37 wherein the non-metal absorbing material is doped vanadium oxide and wherein the reflectance spectrum may be varied with temperature.

42. The device of claim 37 wherein the non-metal absorbing material is a substoichiometric metal oxide.

43. The device of claim 42 wherein the substoichiometric metal oxide is TiO_x.

44. A multi layer interference device, having a reflectance spectrum in the visible wavelength region comprising at least one maximum, comprising;

at least one multilayer stack,

a reflective layer having at least one surface for carrying said at least one multi layer stack,

said at least one multi layer stack comprises a layer of dielectric material and a layer of absorbing material,

such that incident electromagnetic radiation, having a wavelength at which odd multiples of quarter wavelengths substantially correspond to the optical thickness of said at least one multi layer stack at said wavelength, is substantially absorbed within the device, wherein the absorbing material is a conducting substoichiometric metal oxide.