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Selective Functionalization of OWL
Nanostrutures Using Simple Wet-Etchant
Techniques
William A. Gallopp, Skidmore College
Matthew J. Rycenga, Chemisty
Chad A. Mirkin, Chemistry
Northwestern University
Outline
• Motivation and strategy of selective functionalization
• Fabrication of nanorods (On Wire Lithography)
• Optimized etchant parameters
• Energy Dispersive Spectroscopy analysis of
selectively functionalized rods
What is Selective Functionalization?
The ability to control the molecular coverage
of a nanoparticle surface.
Selective Functionalization is Critical to
Nanotechnology
P. Muhlschlegel, et al. Science, 2005, 308, 1607Y. Xia, et al. Adv. Mater., 2008, 308, 1607
Etching Sonication
1. Dissolve Template
(NaOH )
Electrochemical Synthesis
Au or Ag
Ni
Au/Ti or SiO2
2. Disperse rods on Glass
Slides
Deposit Backing
(SiO2, metals)
Mirkin and coworkers, Science
On-Wire Lithography (OWL)
(Alumina Membrane)
HNO3
NaOH
Ag Evaporation
Ag Electrodeposition
Rinse
New Plating Sol’n
Reference electrode
Counter electrode
Working electrode
Rinse
New Plating Sol’n
Nanorod Fabrication
Length: 380 nm Au segment: 100 nm and 200 nm
Diameter: 55 nm Ni segment : 80 nm
Scale bars = 300 nm (top)
100 nm (bottom)
Nano Lett. 2007, 7, 3849
Currently No Control Over Functionalization
Proposed Strategy for Selective Functionalization
= Streptavidin-FeO3NPs (d = 10 nm)
HS O
O
O
O
O
O
N
H
O
S
NH
HN
O
Biotin thiol
MHA (Hydroxy thiol)
Monitoring Etching process by UV-Vis: Unprotected
Rods
Unetched Rods
Etched Rods
200 nm
500 nm
Monitoring Etching process by UV-Vis: Unprotected
Rods vs. Coated Rods
2.76mM HCl solution
MHA Coated Rods
Unprotected Rods
200 nm
200 nm
MHA Coated Rods require longer etch times and
higher HCl concentration
27.7 mM HCl solution
1.0 -1.5 hrs
500 nm 2.00 um200 nm
Energy-Dispersive X-Ray Spectroscopy (EDS)
EDS for Identification of FeO
Au Ni FeImage
Summary
• Importance of selective functionalize
• OWL and selective functionalization processes
• Optimized etchant parameters
• EDS Analysis of functionalized rods
Future work
• Optimize biotin/streptadvin coupling
• EDS confirmation of selective functionalization
• Deposit silica backing to nanorods (OWL)
• Selectively functionalize rods with DNA
Acknowledgements
• Prof. Chad Mirkin
• Dr. Matthew Rycenga
• Dr. Chad Shade
• Dr. Gilles Bourret
• NSF
EDS: Fe Particles

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Will- 2012 REU Symposium Presentation

  • 1. Selective Functionalization of OWL Nanostrutures Using Simple Wet-Etchant Techniques William A. Gallopp, Skidmore College Matthew J. Rycenga, Chemisty Chad A. Mirkin, Chemistry Northwestern University
  • 2. Outline • Motivation and strategy of selective functionalization • Fabrication of nanorods (On Wire Lithography) • Optimized etchant parameters • Energy Dispersive Spectroscopy analysis of selectively functionalized rods
  • 3. What is Selective Functionalization? The ability to control the molecular coverage of a nanoparticle surface.
  • 4. Selective Functionalization is Critical to Nanotechnology P. Muhlschlegel, et al. Science, 2005, 308, 1607Y. Xia, et al. Adv. Mater., 2008, 308, 1607
  • 5. Etching Sonication 1. Dissolve Template (NaOH ) Electrochemical Synthesis Au or Ag Ni Au/Ti or SiO2 2. Disperse rods on Glass Slides Deposit Backing (SiO2, metals) Mirkin and coworkers, Science On-Wire Lithography (OWL)
  • 6. (Alumina Membrane) HNO3 NaOH Ag Evaporation Ag Electrodeposition Rinse New Plating Sol’n Reference electrode Counter electrode Working electrode Rinse New Plating Sol’n Nanorod Fabrication
  • 7. Length: 380 nm Au segment: 100 nm and 200 nm Diameter: 55 nm Ni segment : 80 nm
  • 8. Scale bars = 300 nm (top) 100 nm (bottom) Nano Lett. 2007, 7, 3849 Currently No Control Over Functionalization
  • 9. Proposed Strategy for Selective Functionalization = Streptavidin-FeO3NPs (d = 10 nm) HS O O O O O O N H O S NH HN O Biotin thiol MHA (Hydroxy thiol)
  • 10. Monitoring Etching process by UV-Vis: Unprotected Rods Unetched Rods Etched Rods 200 nm 500 nm
  • 11. Monitoring Etching process by UV-Vis: Unprotected Rods vs. Coated Rods 2.76mM HCl solution MHA Coated Rods Unprotected Rods 200 nm 200 nm
  • 12. MHA Coated Rods require longer etch times and higher HCl concentration 27.7 mM HCl solution 1.0 -1.5 hrs 500 nm 2.00 um200 nm
  • 14. EDS for Identification of FeO Au Ni FeImage
  • 15. Summary • Importance of selective functionalize • OWL and selective functionalization processes • Optimized etchant parameters • EDS Analysis of functionalized rods
  • 16. Future work • Optimize biotin/streptadvin coupling • EDS confirmation of selective functionalization • Deposit silica backing to nanorods (OWL) • Selectively functionalize rods with DNA
  • 17. Acknowledgements • Prof. Chad Mirkin • Dr. Matthew Rycenga • Dr. Chad Shade • Dr. Gilles Bourret • NSF