Methods to fabricate vertically oriented anatase nanowire arrays on transparent conductive substrates and applications thereof

• US 8,835,285 B2
• Filed: 08/21/2012
• Issued: 09/16/2014
• Est. Priority Date: 08/22/2011
• Status: Active Grant

• Current Assignee: Comstock IP Holdings LLC
• Original Assignee: Flux Photon Corporation
• Inventors: Grimes, Craig A., Feng, Xinjian, Kreisler, Kevin E.
• Primary Examiner(s): Sarkar, Asok K
• Application Number:
  US13/590,786
• Publication Number:
  US 20130048947A1
• Time in Patent Office: 756 Days
• Field of Search: 257/E21.09, 257/E29.168, 438/478, 438/962
• US Class Current: 438/478
• CPC Class Codes: B01J 21/063 Titanium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: B01J 35/39 Photocatalytic properties
• CPC Class Codes: B01J 35/58 Fabrics or filaments
• CPC Class Codes: B01J 37/0228 in several steps
• CPC Class Codes: B01J 37/033 Using Hydrolysis
• CPC Class Codes: B01J 37/06 Washing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/346 of microwave energy
• CPC Class Codes: B01J 37/348 Electrochemical processes, e.g. electrochemical deposition or anodisation
• CPC Class Codes: B82Y 10/00 Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• CPC Class Codes: C30B 1/02 by thermal treatment, e.g. strain annealing C30B1/12 takes precedence
• CPC Class Codes: C30B 1/10 by solid state reactions or multi-phase diffusion
• CPC Class Codes: C30B 29/34 Silicates
• CPC Class Codes: C30B 29/602 Nanotubes
• CPC Class Codes: C30B 7/10 by application of pressure, e.g. hydrothermal processes
• CPC Class Codes: H01G 9/2031 comprising titanium oxide, e.g. TiO2 H01G9/2036 takes precedence
• CPC Class Codes: H01L 29/0665 the shape of the body defining a nanostructure nanotechnology per se B82B
• CPC Class Codes: H01L 29/0676 oriented perpendicular or at an angle to a substrate
• CPC Class Codes: H01L 29/127 Quantum box structures

Abstract

The present invention relates to growth of vertically-oriented crystalline nanowire arrays upon a transparent conductive or other substrate for use in 3^rd generation photovoltaic and other applications. A method of growing crystalline anatase nanowires includes the steps of: deposition of titania onto a substrate; conversion of the titania into titanate nanowires; and, treatment of the titanate nanowires to produce crystalline anatase nanowires.

Claims

1. A method of growing crystalline anatase nanowires upon a substrate comprising the steps of:

deposition of a layer of titania onto a substrate;

conversion of the layer of titania into titanate nanowires; and

,

treatment of the titanate nanowires to produce crystalline anatase nanowires.

2. The method of claim 1 wherein one or more reactors are used in one or more steps, simultaneously and/or sequentially, and in a continuous and/or batch manner.

3. The method of claim 2 wherein one or more reactors are heated within a range of temperatures including about 120°

C. to about 340°

C.

4. The method of claim 2 wherein one or more reactors are heated for a duration ranging from about 0.25 h to about 48 h.

5. The method of claim 2 wherein at least one of the reactors is a hydrothermal reactor.

6. The method of claim 2 wherein at least one of the reactors is a microwave-driven hydrothermal reactor.

7. The method of claim 6 wherein a range of microwave power levels in the microwave-driven hydrothermal reactor are used between about 50 W and about 5,000 W.

8. The method of claim 6 wherein a range of microwave-driven reaction times in the microwave-driven hydrothermal reactor treatment is used between about 30 and about 6 h.

9. The method of claim 1 in which one or more solvents are used, either simultaneously or sequentially.

10. The method of claim 9 in which the solvent is comprised at least in part of one or more hydroxides, which are be selected from the group consisting of NaOH, KOH, LiOH, RbOH, Ca(OH)₂ and NH₄OH, to produce a nanowire composition containing the alkali ion of the hydroxide used.

11. The method of claim 9 wherein the solvent molarity is in the range of about 0.5 M to about 18 M.

12. The method of claim 1 wherein the treatment step includes immersion of the titanate nanowires in an acid solution.

13. The method of claim 12 wherein the acid solution is of the molarity range of about 0.01 M to about 5 M.

14. The method of claim 12 wherein the resulting nanowire array is immersed in the acid solution for a duration between about 10 min to about 24 h.

15. The method of claim 1 wherein the treatment step includes annealing of the titanate nanowires.

16. The method of claim 15 wherein the annealing step is completed in the presence of gas.

17. The method of claim 16 wherein the gas utilized in the annealing step is comprised at least in part of oxygen wherein the anatase nanowires are anatase TiO₂ nanowires.

18. The method of claim 15 in which the annealing step is conducted before, during or after acid immersion.

19. The method of claim 15 wherein the nanowires are annealed at temperatures ranging from about 225°

C. to about 600°

C.

20. The method of claim 15 wherein the nanowires are annealed for durations ranging from about 0.1 h to about 48 h.

21. The method of claim 1 wherein the substrate is comprised of one or more types of glass, metal, ceramic, fiber, and/or polymer.

22. The method of claim 1 in which the crystalline anatase nanowires are grown upon one or both sides of the substrate, the substrate being flat.

23. The method of claim 1 in which the crystalline anatase nanowires are grown upon one or more sides of the substrate, where the substrate is a three dimensional structure, the structure constructed in the form of a cylinder, sphere, polyhedron, honeycomb, lattice, or other structures with regular or irregular dimensions.

24. The method of claim 1 in which the substrate is flexible.

25. The method of claim 1 wherein the substrate is comprised of or coated with graphene, or other material comprised at least in part of carbon.

26. The method of claim 1 wherein the substrate is coated on one or more sides with a transparent conductive oxide (“

TCO”

) layer.

27. The method of claim 26 in which the TCO layer is comprised of one or more oxides, which are selected from the group consisting of tin oxide (“

SnO₂”

), indium-doped tin oxide (“

ITO”

), and fluorine-doped tin oxide (“

FTO”

).

28. The method of claim 1 wherein the substrate is modified for chemical and/or physical resistance.

29. The method of claim 1 wherein the substrate is coated on at least one side with a protective layer, which protective layer may be comprised of Polytetrafluoroethylene (“

PTFE”

), poly(methyl methacrylate) (“

PMMA”

) dissolved in acetone, photoresist, a layer of sputtered metal or metals, a sacrificial layer of spin-on glass, or other like protective layer.

30. The method of claim 1 in which one or more of the deposition, conversion and/or treatment steps includes the introduction of one or more dopants, or mixtures thereof, that shift the bandgap energy of the final anatase nanowire array.

31. The method of claim 30 wherein the dopant or dopants are selected from the group consisting of Ag, Al, As, Au, Bi, C, Cd, Co, Cu, Fe, Ga, Ge, In, Ir, N, Ni, Pb, Pd, Pt, Rh, Sb, Si, Sn, Ta, Tl, W, and Zn.

32. The method of claim 1 in which one or more of the deposition, conversion and/or treatment steps includes the introduction of one or more dyes to sensitize the final anatase nanowire array for absorption of radiation.

33. The method of claim 1 in which one or more of the deposition, conversion and/or treatment steps includes the intercalation of quantum dots, of one or more sizes, and of one or more compositions, with or without the use of one or more dyes or other material for absorption of radiation, to sensitize the final anatase nanowire array for absorption of radiation.

34. The method of claim 1 in which one or more of the deposition, conversion and/or treatment steps includes the intercalation of one or more p-type semiconductors within the nanowire arrays, the nanowire arrays being n-type semiconducting anatase.

35. The method of claim 34 wherein the p-type semiconductor is inorganic and/or an organic material, such as a polymer.

36. The method of claim 1 in which any of the deposition, conversion and/or treatment steps, or any aspect of such steps, are completed in one or more steps, in any sequence, at the same time as and/or together with one or more other steps, in a continuous or batch manner, and/or multiple times to iteratively produce the desired final crystalline anatase nanowire array.

37. The method of using the crystalline anatase nanowire array of claim 1 to produce electricity.

38. A device comprised at least in part of the crystalline anatase nanowire array of claim 1 for use in the production of electricity from radiation.

39. The method of using the crystalline anatase nanowire array of claim 1 to catalyze and/or promote chemical reactions.

40. A device comprised at least in part of the crystalline anatase nanowire array of claim 1 for use in the catalysis and/or promotion of chemical reactions with radiation.

41. The method of using the crystalline anatase nanowire array of claim 1 in an energy storage device.

42. A device for energy storage in which one or more electrodes is comprised at least in part of the crystalline anatase nanowire array of claim 1.