Method to fabricate vertically oriented anatase nanowires on a substrate

• US 9,394,623 B2
• Filed: 03/17/2014
• Issued: 07/19/2016
• Est. Priority Date: 08/22/2011
• Status: Expired due to Fees

• Current Assignee: Craig Grimes, Kevin Kreisler, Thomas Latempa
• Original Assignee: Craig Grimes, Kevin Kreisler, Thomas Latempa
• Inventors: Grimes, Craig, Latempa, Thomas, Kreisler, Kevin
• Primary Examiner(s): Sarkar, Asok K
• Application Number:
  US14/215,722
• Publication Number:
  US 20140196658A1
• Time in Patent Office: 855 Days
• Field of Search: None
• US Class Current: 1/1
• 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 fabrication and application of compositions, devices, methods and systems for utilizing radiation more efficiently as compared to known systems. A synthesis method provides deposition of titania on a substrate without the use of an electrochemical reaction. An integrated architecture formed by the method of the present invention is comprised of vertically-oriented, one-dimensional, monocrystalline, n-type anatase nanowires in communication with a common transparent conductive substrate, and which are intercalated with a consortia of p-type quantum dots tuned for absorption of infrared and other radiation.

Claims

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

deposition of titania onto a clean substrate;

conversion of the titania into titanate nanowires; and

,

treatment of the titanate nanowires to produce crystalline anatase nanowires.

2. The method of claim 1 wherein the clean substrate is obtained by the steps of:

placing a substrate into an ultrasonic bath of isopropanol, followed by placing the substrate in ultrasonic bath of acetone, followed by placing the substrate in an ultrasonic bath of methanol, followed by placing the substrate in an ultrasonic bath of water; and

drying the substrate with an inert gas.

3. The method of claim 1 wherein the clean substrate is obtained by the steps of:

sonicating the substrate in a NaOH saturated ethanol solution, rinsing the substrate with de-ionized water; and

drying the substrate with an inert gas.

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

5. The method of claim 4 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.

6. The method of claim 5 wherein the solvent molarity is in the range of about 0.5 M to about 18 M.

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

8. The method of claim 7 wherein the acid solution is of the molarity range of about 0.01 M to about 5 M.

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

10. The method of claim 9 wherein the annealing step is completed in the presence of gas.

11. The method of claim 10 wherein the gas utilized in the annealing step is comprised at least in part of oxygen.

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

13. 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.

14. 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.

15. 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.

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

TCO”

) layer.

17. The method of claim 16 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”

).

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

19. 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.

20. 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.

21. 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.

22. 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.