Chromogenically tunable photonic crystals

• US 20080030837A1
• Filed: 07/30/2007
• Published: 02/07/2008
• Est. Priority Date: 08/01/2006
• Status: Active Grant

• Current Assignee: Universite de Moncton
• Original Assignee: Universite de Moncton
• Inventors: Kuai, Sulan, Ashrit, Pandurang
• Granted Patent: US 7,660,029 B2
• Time in Patent Office: Days
• US Class Current: 359/273
• CPC Class Codes: G02F 1/1524 Transition metal compounds
• CPC Class Codes: G02F 2202/32 Photonic crystals

Abstract

Tunable photonic crystals offer an interesting possibility to adjust the photonic band gap (PBG) as per requirement. Various methods of achieving this have been tried that include polarization of liquid crystals, thermal effects and more. Chromogenic devices provided in accordance with the present invention include combinations and subcombinations of electrochromic, photochromic, thermochromic devices featuring TMO based inverse opals having tunable photonic band gaps (PBG) for certain frequencies. Electrochromic (EC) materials in which a reversible optical property change can be induced with the application of a small electric field offer a novel possibility to tune the PBG in a controlled and reversible way. The reversible chemical change and the ensuing change of optical constants in these periodically arranged EC materials make the PBG tunability possible. In a recent work we have demonstrated for the first time the PBG tunability of EC materials deposited in the form of periodic inverse opals. This earlier work was carried out with the well known Tungsten Trioxide (WO₃) EC thin films into which lithium intercalation was done by a dry lithiation method. In the present work we report on the fabrication of a simple tunable photonic crystal device based on electrochemical insertion/extraction of lithium based on WO₃ inverse opals. In alternative embodiments, any suitable transparent conductor can be utilised instead of Indium Tin Oxide (ITO); any suitable electrochromic transition metal oxide, such as for example Molybdenum Oxide (MoO3), Vanadium Pentoxide (V₂O₅), Titanium Oxide (TiO₂), Chromium Oxide (Cr₂O₃), or Cerium Oxide (CeO₂) can be utilised instead of Tungsten Oxide (WO₃); and any suitable electrolyte solution can be utilised instead of LiClO₄ in Polypropylene Carbonate (LiClO₄/PC) solution.

Claims

1. A method of fabrication of an electrochromically tunable photonic device, the method comprising the steps of:

(a) providing a first transparent conductor coated substrate having a film side comprising the transparent conductor coating;

(b) providing an electrochromic transition metal oxide inverse opal structure;

(c) providing electrolyte solution as a source of metal ions;

(d) providing a second transparent conductor coated substrate having a film side comprising the transparent conductor coating; and

(e) sandwiching the electrochromic transition metal oxide inverse opal structure and the electrolyte solution between the film side of said first transparent conductor coated substrate and the film side of the second transparent conductor coated substrate.

2. The method as recited in claim 1, wherein the transparent conductor is Indium Tin Oxide (ITO).

3. The method as recited in claim 1, wherein the electrochromic transition metal oxide is Tungsten Oxide (WO₃).

4. The method as recited in claim 1, wherein the electrochromic transition metal oxide is Molybdenum Oxide (MoO₃).

5. The method as recited in claim 1, wherein the electrochromic transition metal oxide is Vanadium Pentoxide (V₂O₅).

6. The method as recited in claim 1, wherein the electrochromic transition metal oxide is Chromium Oxide (Cr₂O₃).

7. The method as recited in claim 1, wherein the electrochromic transition metal oxide is Titanium Oxide (TiO₂).

8. The method as recited in claim 1, wherein the electrochromic transition metal oxide is Cerium Oxide (CeO₂).

9. The method as recited in claim 1, wherein the electrolyte solution is a LiClO₄ in Polypropylene Carbonate (LiClO₄/PC) solution.

10. The method as recited in claim 1, wherein the step of providing electrochromic transition metal oxide inverse opal structure comprises the acts of:

(a) providing a polystyrene colloidal crystal template on the film side of the first transparent conductor coated substrate;

(b) providing an electrochromic transition metal oxide sol;

(c) replacing the polystyrene colloidal crystal template with electrochromic transition metal oxide contained in the electrochromic transition metal oxide sol by using the dip-infiltrating sol-gel technique thereby providing the electrochromic transition metal oxide inverse opal structure on the first transparent conductor coated substrate.

11. The method as recited in claim 10, wherein the act of providing colloidal crystal template on the film side of the first transparent conductor coated substrate comprises the acts of:

(a) cleaning the first transparent conductor coated substrate to provide a substrate;

(b) placing the substrate vertically into a vial filled with aqueous solution of polystyrene monodisperse spheres;

(c) maintaining conditions appropriate for the polystyrene colloidal crystal template to grow onto the film side of the substrate.

12. The method as recited in claim 11, wherein the polystyrene monodisperse spheres have a size which is between 200 nm and 400 nm.

13. The method as recited in claim 11, wherein the volume fraction of the aqueous solution is about 1 to 1.5 drop of 10% polystyrene spheres per 5 ml water.

14. The method as recited in claim 11, wherein temperature is maintained at about 60°

C.

15. The method as recited in claim 11, wherein a period during which the conditions are maintained is about a week.

16. The method as recited in claim 11, wherein the polystyrene monodisperse spheres have a size which is above 600 nm.

17. The method as recited in claim 16, wherein a temperature gradient is applied across the vial by placing the vial in a sand bath on a hot plate.

18. The method as recited in claim 10, wherein the act of providing an electrochromic transition metal oxide sol comprises the acts of:

(a) dissolving metallic electrochromic transition metal in Hydrogen peroxide and acetic acid to form a solution;

(b) filtering the solution;

(c) evaporating the solution to dryness resulting in an electrochromic transition metal peroxy acid powder;

(d) reacting the electrochromic transition metal peroxy acid powder with ethanol to form the electrochromic transition metal oxide sol comprising a electrochromic transition metal peroxyester derivative dipping solution; and

(e) removing any precipitate from the electrochromic transition metal oxide sol.

19. The method as recited in claim 10, wherein the act of replacing the polystyrene colloidal crystal template with electrochromic transition metal contained in the electrochromic transition metal oxide sol comprises the acts of:

(a) immersing the polystyrene colloidal crystal template on the film side of the first transparent conductor coated substrate vertically in the electrochromic transition metal oxide sol so that the electrochromic transition metal oxide sol penetrates the voids in the template due to capillary forces thereby providing a sample;

(b) removing the sample from the electrochromic transition metal oxide sol;

(c) gelating the electrochromic transition metal oxide sol which penetrated the voids in the template of the sample;

(d) drying the sample the sample thereby resulting in a polystyrene-gel composite;

(e) optionally repeating acts a-d so as to incorporate more material into the template; and

(f) sintering the resulting polystyrene-gel composite to remove the polystyrene template thereby leaving a fully porous electrochromic transition metal inverse opal structure.

20. The method as recited in claim 19, wherein the act of immersing is conducted for about 5 minutes.

21. The method as recited in claim 19, wherein the act of drying occurs at about 80°

C. for about half an hour.

22. The method as recited in claim 19, wherein the act of sintering occurs at about 460°

C. for about an hour.

23. The method as recited in claim 1, further comprising, prior to the sandwiching step, a step of inserting lithium atoms in the inverse opal structure to facilitate the fabrication and to optimize the lithium content thereby improving the coloration of the device.

24. The method as recited in claim 23, wherein the inserting lithium atoms step comprises a lithination act carried out by one of a dry in-situ method and a wet method.

25. The method as recited in claim 1, wherein the sandwiching step comprises the acts of:

(a) providing a plastic spacer between the first and second transparent conductor coated substrate so as to create a channel to receive the electrolyte solution;

(b) applying a small pressure onto the sandwiched structure while heating to melt the spacer and fuse the structure together while leaving a small opening for the channel in the spacer;

(c) sucking the electrolyte solution into the sandwiched structure under vacuum through the small opening left in the spacer; and

(d) blocking the small opening in the spacer to prevent leakage of the electrolyte solution.

26. An electrochromically tunable photonic crystal device comprising:

(a) a first Indium Tin Oxide (ITO) substrate having a film side comprising the ITO coating, the film side capable of acting as a first electrode;

(b) an WO₃ inverse opal layer structure provided in contact with the film side of the first ITO substrate;

(c) a LiClO₄ in Polypropylene Carbonate (LiClO₄/PC) solution provided in contact with the WO₃ inverse opal structure; and

(d) a second ITO substrate having a film side comprising the ITO coating, the film side capable of acting as a second electrode in contact with the LiClO₄/PC solution;

whereby the application of an electric field between the first and second electrodes would result in reversible coloration by reversible formation of tungsten bronze (Li_xWO₃) as follows;

WO₃ (transparent)+xe⁻

+xLi⁺⇄

Li_xWO₃ (blue).

27. The device as recited in claim 26, further comprising means for biasing coloration wherein a negative polarity is applied at the first electrode relative to the second electrode such that electrons and lithium ions are biased to be injected into the WO₃ periodic structure.

28. The device as recited in claim 26, further comprising means for biasing bleaching wherein a positive polarity is applied at the first electrode relative to the second electrode such that electrons and lithium ions are biased to be extracted from the WO₃ periodic structure.

29. The device as recited in claim 26, wherein the electric field is caused by a double insertion potential of about −

4V applied between the first electrode and the second electrode.

30. The device as recited in claim 26, wherein the electric field is caused by an extraction potential of about +4V applied between the first electrode and the second electrode.

31. The device as recited in claim 26, wherein the electric field is caused by an extraction potential which is proportional to the thickness of the device.

32. The device as recited in claim 26, further comprising a spacer to form a channel in the device to hold the LiClO₄/PC solution.

33. The device as recited in claim 32, wherein the spacer is about a couple of microns thick.

34. An electrochromically tunable photonic device comprising:

(a) a first transparent conductor coated substrate having a film side comprising the transparent conductor coating, the film side capable of acting as a first electrode;

(b) an electrochromic transition metal oxide inverse opal layer structure provided in contact with the film side of the first transparent conductor coated substrate;

(c) an electrolyte solution as a source of metal ions provided in contact with the electrochromic transition metal oxide inverse opal structure; and

(d) a second transference substrate having a film side comprising the transparent conductor coating, the film side capable of acting as a second electrode in contact with the electrolyte solution;

whereby the application of an electric field between the first and second electrodes would result in reversible coloration by reversible reaction as follows;

[electrochromic transition metal oxide] (bleached/colored)+xe⁻

+x[metal ion]⁺⇄

[metal ion]_x[electrochromic transition metal oxide] (colored/bleached).

35. The method as recited in claim 34, wherein the transparent conductor is Indium Tin Oxide (ITO).

36. The method as recited in claim 34, wherein the electrochromic transition metal oxide is Tungsten Oxide (WO₃).

37. The method as recited in claim 34, wherein the electrochromic transition metal oxide is Molybdenum Oxide (MoO₃).

38. The method as recited in claim 34, wherein the electrochromic transition metal oxide is Vanadium Pentoxide (V₂O₅).

39. The method as recited in claim 34, wherein the electrochromic transition metal oxide is Chromium Oxide (Cr₂O₃).

40. The method as recited in claim 34, wherein the electrochromic transition metal oxide is Titanium Oxide (TiO₂).

41. The method as recited in claim 34, wherein the electrochromic transition metal oxide is Cerium Oxide (CeO₂).

42. The method as recited in claim 34, wherein the electrolyte solution is a LiClO₄ in Polypropylene Carbonate (LiClO₄/PC) solution.

43. The device as recited in claim 34, further comprising means for biasing coloration wherein a negative polarity is applied at the first electrode relative to the second electrode such that electrons and metal ions are biased to be injected into the inverse opal periodic structure.

44. The device as recited in claim 34, further comprising means for biasing bleaching wherein a positive polarity is applied at the first electrode relative to the second electrode such that electrons and metal ions are biased to be extracted from the inverse opal periodic structure.

45. The device as recited in claim 34, wherein the electric field is caused by a double insertion potential of about −

4V applied between the first electrode and the second electrode.

46. The device as recited in claim 34, wherein the electric field is caused by an extraction potential of about +4V applied between the first electrode and the second electrode.

47. The device as recited in claim 34, wherein the electric field is caused by an extraction potential which is proportional to the thickness of the device.

48. The device as recited in claim 34, further comprising a spacer to form a channel in the device to hold the electrolyte solution.

49. A chromogenically tunable photonic crystal device comprising:

(a) a substrate;

(b) a transition metal oxide inverse opal layer structure provided in contact with the substrate;

whereby the application of an external stimuli results in reversible coloration of the transition metal oxide inverse opal layer structure.

50. The device as recited in claim 49, wherein the external stimuli is an electric field.

51. The device as recited in claim 49, wherein the external stimuli is heat.

52. The device as recited in claim 49, wherein the external stimuli is light.