IP Library Granted Patent US 9,778,197
Granted Patent B2
US 9,778,197 · App. 14/450,633 · Granted Oct 3, 2017

Metal-dielectric-CNT nanowires for surface-enhanced Raman spectroscopy

Inventors: Tiziana C. Bond (Livermore, CA); Ali Altun (Zurich, CH); Hyung Gyu Park (Zurich, CH)
Assignees: Lawrence Livermore National Security, LLC; ETH Zurich
G01N21/658C23C16/045C23C16/405C23C16/45555C30B25/18C30B29/16C30B29/60C30B29/602
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Quick Facts
Patent No.
US 9,778,197
App. No.
14/450,633
Granted
Oct 3, 2017
Kind
B2
Abstract

A sensor with a substrate includes nanowires extending vertically from the substrate, a hafnia coating on the nanowires that provides hafnia coated nanowires, and a noble metal coating on the hafnia coated nanowires. The top of the hafnia and noble metal coated nanowires bent onto one another to create a canopy forest structure. There are numerous randomly arranged holes that let through scattered light. The many points of contact, hot spots, amplify signals. The methods include the steps of providing a Raman spectroscopy substrate, introducing nano crystals to the Raman spectroscopy substrate, growing a forest of nanowires from the nano crystals on the Raman spectroscopy substrate, coating the nanowires with hafnia providing hafnia coated nanowires, and coating the hafnia coated nanowires with a noble metal or other metal.

Claims (41)

1. A method of making a substrate for surface enhanced Raman spectroscopy, comprising the steps of:

providing a Raman spectroscopy substrate,

introducing nano crystals directly onto said Raman spectroscopy substrate,

growing a forest of nanowires from said nano crystals that have been introduced directly onto said Raman spectroscopy substrate, said step of growing a forest of nanowires from said nano crystals comprising growing a forest of nanowires extending vertically from said nanocrystals and extending vertically from said Raman spectroscopy substrate wherein said nanowires have

vertical sections of said nanowires wherein said vertical sections extend vertically from said Raman spectroscopy substrate and

top parts of said nanowires connected to said vertical sections of said nanowires wherein said top parts of said nanowires form bent ends of said nanowires that extend horizontally and parallel to said Raman spectroscopy substrate,

coating said nanowires including said vertical sections and said bent ends with hafnia providing hafnia coated nanowires, hafnia coated vertical sections, and hafnia coated bent ends,

coating said hafnia coated nanowires with a noble metal providing noble metal and hafnia coated nanowires, noble metal and hafnia coated vertical sections, and noble metal and hafnia coated bent ends, and

forming a canopy of said noble metal and hafnia coated bent ends of said noble metal and hafnia coated nanowires that extends horizontally and parallel to said Raman spectroscopy substrate.

2. The method of making a substrate for surface enhanced Raman spectroscopy of claim 1 wherein said step of forming a canopy of said noble metal and hafnia coated bent ends includes allowing holes to be formed between said bent ends.

3. The method of making a substrate for surface enhanced Raman spectroscopy of claim 1 wherein said step of forming a canopy of said noble metal and hafnia coated bent ends includes allowing points of contact of said bent ends to be formed.

4. A surface enhanced Raman spectroscopy substrate apparatus, comprising:

a Raman spectroscopy substrate,

nanowires extending vertically from said Raman spectroscopy substrate, wherein said nanowires have

vertical sections of said nanowires wherein said vertical sections extend vertically from said Raman spectroscopy substrate and

top parts of said nanowires connected to said vertical sections of said nanowires wherein said top parts of said nanowires form bent ends of said nanowires that extend horizontally and parallel to said Raman spectroscopy substrate,

a hafnia coating on said nanowires that provides hafnia coated nanowires including hafnia coated vertical sections of said nanowires and hafnia coated bent ends of said nanowires,

a noble metal coating on said hafnia coated nanowires that provides noble metal coated hafnia coated vertical sections of said nanowires and noble metal coated hafnia coated bent ends of said nanowires, and

a canopy of said noble metal coated hafnia coated bent ends of said nanowires that extend horizontally and parallel to said Raman spectroscopy substrate wherein said noble metal coated hafnia coated bent ends of said nanowires forms said canopy that extend horizontally and parallel to said Raman spectroscopy substrate.

5. The surface enhanced Raman spectroscopy substrate apparatus of claim 4 wherein said canopy of bent ends includes holes between said bent ends.

6. A method of making a substrate for surface enhanced Raman spectroscopy, comprising the steps of:

providing a Raman spectroscopy substrate,

introducing nano crystals directly onto said Raman spectroscopy substrate,

growing a forest of nanowires from said nano crystals that have been introduced directly onto said Raman spectroscopy substrate, said step of growing a forest of nanowires from said nano crystals comprising growing a forest of nanowires extending vertically from said nanocrystals and extending vertically from said Raman spectroscopy substrate wherein said nanowires have

vertical sections of said nanowires wherein said vertical sections extend vertically from said Raman spectroscopy substrate and

top parts of said nanowires connected to said vertical sections of said nanowires wherein said top parts of said nanowires form bent ends of said nanowires that extend horizontally and parallel to said Raman spectroscopy substrate,

coating said nanowires including said vertical sections and said bent ends with hafnia providing hafnia coated nanowires, hafnia coated vertical sections, and hafnia coated bent ends,

coating said hafnia coated nanowires with a gold coating that has a thickness of between ten and one half nanometers and twenty one nanometers providing gold and hafnia coated nanowires, gold and hafnia coated vertical sections, and gold and hafnia coated bent ends with a total gold-hafnia-nanowire thickness that lies between thirty five nanometers and fifty six nanometers,

forming a canopy of said gold and hafnia coated bent ends of said gold and hafnia coated nanowires that extends horizontally and parallel to said Raman spectroscopy substrate,

forming a multiplicity of holes in said canopy extending from said canopy toward said Raman spectroscopy substrate where said multiplicity of holes are located between said gold coated hafnia coated vertical sections of said nanowires, and

forming many points of contact between said gold coated hafnia coated vertical sections of said nanowires located in said multiplicity of holes wherein said many points of contact provide electromagnetic enhancement.

7. A surface enhanced Raman spectroscopy substrate apparatus, comprising:

a Raman spectroscopy substrate,

nanowires extending vertically from said Raman spectroscopy substrate, wherein said nanowires have

vertical sections of said nanowires wherein said vertical sections extend vertically from said Raman spectroscopy substrate and

top parts of said nanowires connected to said vertical sections of said nanowires wherein said top parts of said nanowires form bent ends of said nanowires that extend horizontally and parallel to said Raman spectroscopy substrate,

a hafnia coating on said nanowires that provides hafnia coated nanowires including hafnia coated vertical sections of said nanowires and hafnia coated bent ends of said nanowires,

a gold coating on said hafnia coated nanowires that has a thickness of between ten and one half nanometers and twenty one nanometers that provides gold coated hafnia coated vertical sections of said nanowires with a total gold-hafnia-nanowire thickness that lies between thirty five nanometers and fifty six nanometers and gold coated hafnia coated bent ends of said nanowires,

a canopy of said gold coated hafnia coated bent ends of said nanowires that extend horizontally and parallel to said Raman spectroscopy substrate wherein said gold coated hafnia coated bent ends of said nanowires forms said canopy that extend horizontally and parallel to said Raman spectroscopy substrate,

a multiplicity of holes in said canopy extending from said canopy toward said substrate where said multiplicity of holes are located between said gold coated hafnia coated vertical sections of said nanowires, and

many points of contact between said gold coated hafnia coated vertical sections of said nanowires located in said multiplicity of holes wherein said many points of contact provide electromagnetic enhancement.

Assignments (3)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 14, 2015
From: PARK, HYUNG GYU; ALTUN, ALI OZHAN
To: ETH ZURICH
Reel/Frame 037284/0694 →
CONFIRMATORY LICENSE Recorded Apr 15, 2015
From: LAWRENCE LIVERMORE NATIONAL SECURITY, LLC
To: U.S. DEPARTMENT OF ENERGY
Reel/Frame 035409/0945 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 4, 2014
From: BOND, TIZIANA C.
To: LAWRENCE LIVERMORE NATIONAL SECURITY, LLC
Reel/Frame 033458/0924 →
Continuity (2)
Provisional Application 61862405 · Aug 5, 2013
Related Publication 20150036132A1 · Feb 5, 2015